Compositions having improved bath life

ABSTRACT

A composition comprising (A) at least one compound having at least one aliphatic unsaturation; (B) at least one organohydrogensilicon compound containing at least one silicon-bonded hydrogen atom per molecule and (C) a platinum group metal-containing catalyst.

CROSS REFERENCES TO RELATED APPLICATIONS

The present application is a US national stage filing under 35 USC 371and claims priority from PCT application No. PCT/USS03/13214 filed onApr. 29, 2003 and U.S. application No. 60/377,505 filed on May 1, 2002.The above applications are incorporated by reference in their entirety.

This invention relates to a composition comprising (A) at least onecompound having at least one aliphatic unsaturation; (B) at least oneorganohydrogensilicon compound containing at least one silicon-bondedhydrogen atom per molecule and (C) a platinum group metal-containingcatalyst.

Silicon-based compositions which cure by hydrosilylation are useful in awide variety of applications to produce coatings, elastomers, adhesives,foams or fluids. In the silicone release coating area, siliconecompositions are useful in applications where relatively non-adhesivesurfaces are required. Single sided liners, for example, backing papersfor pressure sensitive adhesive labels, are usually adapted totemporarily retain the labels without affecting the adhesive propertiesof the labels. Double sided liners for example, interleaving papers fordouble sided and transfer tapes, are utilized to ensure the protectionand desired unwind characteristics of a double sided self-adhesive tapeor adhesive film. A substrate, for example a single sided liner, iscoated by applying a silicon-based release coating composition onto thesubstrate and subsequently curing the composition, by, for example,thermally initiated hydrosilylation.

The basic constituents of silicon-based compositions which cure byhydrosilylation are an alkenylated polydiorganosiloxane, typically alinear polymer with terminal alkenyl groups; apolyorganohydrogensiloxane cross-linking agent designed to cross-linkthe alkenylated polydiorganosiloxane; and a catalyst, to catalyze theaforementioned cross-linking reaction. Often a fourth constituent, aninhibitor designed to prevent the commencement of curing below aprerequisite cure temperature, is also included in the composition.

Silicon-based release coating compositions having the three essentialconstituents and optionally the inhibitor are generally referred to aspremium release coating compositions. In order to control the level ofrelease force from a release coating it has become common practice for asilicon-based release coating composition to contain an additive,generally known as a release modifier. The release modifier usuallyreplaces a proportion of the alkenylated polydiorganosiloxane in apremium release coating composition.

Improvements in the performance of compositions which cure byhydrosilylation are continuously being sought with respect to, forexample, ease of cure, i.e. the decrease in cure times at relatively lowtemperatures, extended working time of a formulated bath, i.e. longerthin film and bulk bath life, anchorage of coatings to a substrate, andparticularly for high catalyst coatings such as release coatings,maintenance of excellent performance in the aforementioned areas withdecreased catalyst level and therefore decreased cost.

One object of the present invention is to describe compositions withimproved bath life while maintaining excellent cure and anchorageproperties. Another object is to describe compositions that have theabove-described properties even at reduced catalyst levels.

The present invention relates to a composition comprising (A) at leastone compound having at least one aliphatic unsaturation; (B) at leastone organohydrogensilicon compound containing at least onesilicon-bonded hydrogen atom per molecule and (C) a platinum groupmetal-containing catalyst.

The present invention relates to a composition comprising (A) at leastone compound having at least one aliphatic unsaturation; (B) at leastone organohydrogensilicon compound containing at least onesilicon-bonded hydrogen atom per molecule described by formula (III)

where each R is independently selected from a hydrogen atom and amonovalent hydrocarbon group comprising 1 to 20 carbon atoms which isfree from aliphatic unsaturation, a is an integer from 1 to 18, b is aninteger from 1 to 19, a+b is an integer from 3 to 20, each X is anindependently selected functional group selected from a halogen atom, anether group, an alkoxy group, an alkoxyether group, an acyl group, anepoxy group, an amino group, or a silyl group, or a -Z-R⁴ group, whereeach Z is independently selected from an oxygen and a divalenthydrocarbon group comprising 2 to 20 carbon atoms, each R⁴ group isindependently selected from —BR_(u)Y_(2-u), —SiR_(v)Y_(3-v), or a groupdescribed by formula (IV):(Y_(3-n)R_(n)SiO_(1/2))_(c)(Y_(2-o)R_(o)SiO_(2/2))_(d)(Y_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)Y_(1-q))_(g)(CR_(r)Y_(2-r))_(h)(O(CR_(s)Y_(2-s))_(i)(CR_(t)Y_(3-t))_(j)where B refers to boron, each R is as described above, the sum ofc+d+e+f+g+h+i+j is at least 2, n is an integer from 0 to 3, o is aninteger from 0 to 2, p is an integer from 0 to 1, q is an integer from 0to 1, r is an integer from 0 to 2, s is an integer from 0 to 2, t is aninteger from 0 to 3, u is an integer from 0 to 2, v is an integer from 0to 3, each Y is an independently selected functional group selected froma halogen atom, an ether group, an alkoxy group, an alkoxyether group,an acyl group, an epoxy group, an amino group, or a silyl group, or aZ-G group, where Z is as described above, each G is a cyclosiloxanedescribed by formula (V):

where R and X are as described above, k is an integer from 0 to 18, m isan integer from 0 to 18, k+m is an integer from 2 to 20, provided informula (IV) that one of the Y groups is replaced by the Z group bondingthe R⁴ group to the cyclosiloxane of formula (III), and provided furtherif g+h+i+j>0 then c+d+e+f>0; and (C) a platinum group metal-containingcatalyst.

Another embodiment of the present invention is a composition comprising(A) at least one compound having at least one aliphatic unsaturation;(B) at least one organohydrogensilicon compound containing at least onesilicon-bonded hydrogen atom per molecule described by formula (III)

where each R is independently selected from a hydrogen atom and amonovalent hydrocarbon group comprising 1 to 20 carbon atoms which isfree from aliphatic unsaturation, a is an integer from 1 to 18, b is aninteger from 2 to 19, a+b is an integer from 3 to 20, each X is anindependently selected functional group selected from a halogen atom, anether group, an alkoxy group, an alkoxyether group, an acyl group, anepoxy group, an amino group, or a silyl group, or a -Z-R⁴ group, whereeach Z is independently selected from an oxygen and a divalenthydrocarbon group comprising 2 to 20 carbon atoms, each R⁴ group isindependently selected from —BR_(u)Y_(2-u), —SiR_(v)Y_(3-v), or a groupdescribed by formula (IV):(Y_(3-n)R_(n)SiO_(1/2))_(c)(Y_(2-o)R_(o)SiO_(2/2))_(d)(Y_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)Y_(1-q))_(g)(CR_(r)Y_(2-r))_(h)(O(CR_(s)Y_(2-s))_(i)(CR_(t)Y_(3-t))_(j)where B refers to boron, each R is as described above, the sum ofc+d+e+f+g+h+i+j is at least 2, n is an integer from 0 to 3, o is aninteger from 0 to 2, p is an integer from 0 to 1, q is an integer from 0to 1, r is an integer from 0 to 2, s is an integer from 0 to 2, t is aninteger from 0 to 3, u is an integer from 0 to 2, v is an integer from 0to 3, each Y is an independently selected functional group selected froma halogen atom, an ether group, an alkoxy group, an alkoxyether group,an acyl group, an epoxy group, an amino group, or a silyl group, or aZ-G group, where Z is as described above, each G is a cyclosiloxanedescribed by formula (V):

where R and X are as described above, k is an integer from 0 to 18, m isan integer from 0 to 18, k+m is an integer from 2 to 20, provided informula (IV) that one of the Y groups is replaced by the Z group bondingthe R⁴ group to the cyclosiloxane of formula (III), and provided furtherif g+h+i+j>0 then c+d+e+f>0; and (C) a platinum group metal-containingcatalyst.

As used herein, the term “aliphatic unsaturation” refers to acarbon-carbon multiple bond. Further as used herein, the term“compound”, unless indicated otherwise, is a chemical substance whichhas a particular molecular identity or is made of a mixture of suchsubstances, e.g., polymeric substances. The term “hydrosilylation” meansthe addition of organosilicon compounds containing silicon-bondedhydrogen to a compound containing an aliphatic unsaturation, and in thehydrosilylation process described in this application, it refers tothose processes in which platinum group-containing catalysts are used toeffect the addition of an organosilicon compound having a silicon-bondedhydrogen atom to an aliphatically unsaturated compound having eitherolefinic or acetylenic unsaturation.

Component (A) comprises at least one compound having at least onealiphatic unsaturation. The compounds of Component (A) can be linear,branched, resinous or cyclic and can be monomers or polymers (includingcopolymers, terpolymers etc.) provided there is at least one aliphaticunsaturation. Compounds containing aliphatic unsaturation which areuseful in the present invention have alkenyl (also described asolefinic) unsaturation or alkynyl (also described as acetylenic)unsaturation. These compounds are well-known in the art ofhydrosilylation and are disclosed in such patents as U.S. Pat. No.3,159,662 (Ashby), U.S. Pat. No. 3,220,972 (Lamoreaux)), and U.S. Pat.No. 3,410,886 (Joy), which disclosures of said compounds areincorporated herein by reference. In instances where these unsaturatedcompounds contain elements other than carbon and hydrogen, it ispreferred that these elements be oxygen, nitrogen, silicon, a halogen,or a combination thereof.

The aliphatically unsaturated compound of component (A) can contain oneor more carbon-to-carbon multiple bonds. Representative examples of thealiphatically unsaturated hydrocarbons which can be employed includemono-olefins, for example, ethene (ethylene), propene, and 1-pentene,diolefins, for example, divinylbenzene, butadiene, 1,5-hexadiene and1-buten-3-yne, cycloolefins, for example, cyclohexene and cycloheptene,and monoalkynes, for example, acetylene, propyne and 1-hexyne.

Oxygen-containing aliphatically unsaturated compounds can also be usedfor component (A), especially where the unsaturation is ethylenic, suchas vinylcyclohexyl epoxide, allyl glycidyl ether, methylvinyl ether,divinylether, phenylvinyl ether, monoallyl ether of ethylene glycol,allyl aldehyde, methylvinyl ketone, phenylvinyl ketone, acrylic acid,methacrylic acid, methyl acrylate, allyl acrylate, methyl methacrylate,allyl methacrylate, vinylacetic acid, vinyl acetate, and linolenic acid.

Heterocyclic compounds containing aliphatic unsaturation in the ring,such as dihydrofuran, and dihydropyran, are also suitable as component(A) for the present invention.

Halogenated derivatives of the previously mentioned aliphaticallyunsaturated compounds can be employed as component (A), including acylchlorides as well as compounds containing a halogen substituent on acarbon atom other than a carbonyl carbon atom. Such halogen-containingcompounds include, for example, vinyl chloride, and thevinylchlorophenyl esters.

Unsaturated compounds containing nitrogen substituents such asacrylonitrile, N-vinylpyrrolidone, alkyl cyanide, nitroethylene, etc.,are also useful in the practice of the present invention.

Other compounds useful as component (A) in the practice of the presentinvention include polymers (including copolymers, terpolymers etc.) ofthe various compounds described above provided there is at least onealiphatic unsaturation. Examples include polymers derived from olefinicmonomers having 2 to 20 carbon atoms and dienes having 4 to 20 carbonatoms; polymers of monoolefin, isomonoolefin and vinyl aromaticmonomers, such as monoolefins having 2 to 20 carbon groups,isomonoolefins having 4 to 20 carbon groups, and vinyl aromatic monomersincluding styrene, para-alkylstyrene, para-methylstyrene. The compoundscan also be poly(dienes) and derivatives. Most polymers derived fromdienes usually contain unsaturated ethylenic units on backbone orside-chains. Representative examples include polybutadiene,polyisoprene, polybutenylene, poly(alkyl-butenylene) where alkylincludes alkyl groups having 1 to 20 carbon atoms,poly(phenyl-butenylene), polypentenylene, natural rubber (a form ofpolyisoprene); and butyl rubber (copolymer of isobutylene and isoprene).

The compounds of component (A) can also be a halogenated olefin polymerhaving aliphatic unsaturation. Representative examples of a halogenatedolefin polymer having aliphatic unsaturation include polymers resultingfrom the bromination of a copolymer of isomonoolefin withpara-methylstyrene to introduce benzylic halogen (as described in U.S.Pat. No. 5,162,445), halogenated polybutadienes, halogenatedpolyisobutylene, poly(2-chloro-1,3-butadiene), polychloroprene (85%trans), poly(1-chloro-1-butenylene) (Neoprene™), and chlorosulfonatedpolyethylene.

The compound of component (A) having aliphatic unsaturation can alsoinclude polymers containing other compounds described above such asvinyl ether groups, acrylate groups, methyacrylate groups, andepoxy-functional groups.

A particularly useful type of compound which can be employed ascomponent (A) in the present invention is that containing silicon, suchas those compounds commonly referred to as organosilicon compounds andsilicon modified organic compounds. The useful organosilicon compoundshave at least one aliphatically unsaturated group attached to siliconper molecule. The aliphatically unsaturated organosilicon compoundsinclude silanes, polysilanes, siloxanes, silazanes, as well as monomericor polymeric materials containing silicon atoms joined together byhydrocarbyl groups such as alkylene or polyalkylene groups or arylenegroups. The silicon-modified organic compounds useful in the presentinvention include organic monomers or polymers such as described abovehaving at least one silicon atom attached as a silane or a siloxanesegment. The silicon-containing units can contain aliphatic unsaturationand can be attached at the terminal and/or pendant positions on theorganic polymer chain or as a copolymer.

Silanes useful in the present invention can be described by formula (I)Q_(4-w)R¹ _(w)Si,where each R¹ is an independently selected monovalent hydrocarbonradical comprising 1 to 20 carbon atoms free from aliphaticunsaturation, each Q is independently selected from a monovalenthydrocarbon group comprising 2 to 20 carbon atoms having at least onealiphatic unsaturation, a monovalent oxyhydrocarbon group comprising 2to 20 carbon atoms having at least one aliphatic unsaturation, a halogenatom, an alkoxy group, or an acyl group, provided at least one Q grouphas at least one aliphatic unsaturation.

Examples of silanes include vinyltrimethoxysilane, vinyltriethoxysilane,vinyltrimethylsilane, vinyldimethylchlorosilane,vinylmethyldichlorosilane, divinyldimethylsilane, diallyldimethylsilane,hexenyldimethylchlorosilane, and hexenylmethyldichlorosilane, andvinyltriacetoxysilane.

Examples of silane-modified organic polymers are silylated polymersderived from olefins, isomonoolefin, dienes, ethylene or propyleneoxides, and vinyl aromatic monomers having 2 to 20 carbon atoms such asthe silane-grafted copolymers of isomonoolefin and vinyl aromaticmonomer as discussed in U.S. Pat. Nos. 6,177,519 and 5,426,167. Otherrepresentative silicon-modified organic polymers are illustrated by, butnot limited to alkenylsiloxy-functional polymers such as vinylsiloxy-,allylsiloxy-, and hexenylsiloxy-organic polymers and siloxane-organicblock copolymers.

Preferred organosilicon polymers and silicon-modified organic polymerscan be described by formula (II):(Q_(3-n′)R¹ _(n′)SiO_(1/2))_(c′)(Q_(2-o′)R¹_(o′)SiO_(2/2))_(d′)(Q_(1-p′)R¹ _(p′)SiO_(3/2))_(e′)(SiO_(4/2))_(f′)(CR²_(q′)(Q_(1-q′))_(g′)(CR² _(r′)Q_(2-r′))_(h′)(O(CR²_(s′)Q_(2-s′))_(i′)(CR² _(t′)Q_(3-t′))_(j′)where each R¹ and Q group is as described above, each R² is anindependently selected hydrogen atom or monovalent hydrocarbon groupcomprising 1 to 20 carbon atoms which are free from aliphaticunsaturation, the sum of c′+d′+e′+f′+g′+h′+i′+j′ is at least 2, n′ is aninteger from 0 to 3, o′ is an integer from 0 to 2, p′ is an integer from0 to 1, q′ is an integer from 0 to 1, r′ is an integer from 0 to 2, s′is an integer from 0 to 2, t′ is an integer from 0 to 3, provided ifg′+h′+i′+j′>0 then c′+d′+e′+f′>0.

In formulas (I) and (II), each R¹ group is an independently selectedmonovalent hydrocarbon group comprising 1 to 20 carbon atoms which arefree from aliphatic unsaturation. Each R¹ group can be linear, branchedor cyclic. R¹ can be unsubstituted or substituted with halogen atoms.The monovalent hydrocarbon group of R¹ can be exemplified by alkylgroups such as methyl, ethyl, propyl, butyl, hexyl, octyl,3,3,3-trifluoropropyl, chloromethyl, and decyl, cycloaliphatic groupssuch as cyclohexyl, aryl groups such as phenyl, tolyl, and xylyl,chorophenyl, and aralkyl groups such as benzyl, styryl andalpha-methylstyryl. It is preferred that each R¹ group is anindependently selected alkyl group comprising 1 to 8 carbon atoms oraryl group comprising 6 to 9 carbon atoms. It is most preferred thateach R¹ group is independently selected from methyl, alpha-methylstyryl,3,3,3-trifluoropropyl and nonafluorobutylethyl. Each R¹ can be identicalor different, as desired.

In formula (II), each R² group is an independently selected hydrogenatom or monovalent hydrocarbon group comprising 1 to 20 carbon atomsfree from aliphatic unsaturation. Each monovalent hydrocarbon groups ofR² can be linear, branched or cyclic. Each monovalent hydrocarbon groupof R² can be unsubstituted or substituted with halogen atoms. Themonovalent hydrocarbon groups of R² are exemplified as described abovefor the monovalent hydrocarbon groups of R¹. It is preferred that eachR² group is an independently selected hydrogen atom, alkyl groupcomprising 1 to 8 carbon atoms, or aryl group comprising 6 to 9 carbonatoms. It is most preferred that each R² is hydrogen. Each R² can beidentical or different, as desired.

In formulas (I) and (II), each Q is independently selected from amonovalent hydrocarbon group comprising 2 to 20 carbon atoms having atleast one aliphatic unsaturation, a monovalent oxyhydrocarbon groupcomprising 2 to 20 carbon atoms having at least one aliphaticunsaturation, a halogen atom, an alkoxy group, or an acyl group,provided at least one Q group has at least one aliphatic unsaturation.

The aliphatic unsaturations of Q can be found in a pendant position tothe hydrocarbon chain, at the end of the hydrocarbon chain, or both,with the terminal position being preferred. Each monovalent hydrocarbonand oxyhydrocarbon group can be linear, branched, or cyclic.

Examples of monovalent hydrocarbon groups comprising 2 to 20 carbonatoms having at least one aliphatic unsaturation of Q include alkenylgroups such as vinyl, allyl, 3-butenyl, 4-pentenyl, 5-hexenyl,cyclohexenyl, 6-heptenyl, 7-octenyl, 8-nonenyl, 9-decenyl, 10-undecenyl,and diene groups comprising 4 to 20 carbon atoms such as 4,7-octadienyl,5,8-nonadienyl, 5,9-decadienyl, 6,11-dodecadienyl, 4,8-nonadienyl, and7,13-tetradecadienyl.

Examples of monovalent oxyhydrocarbon groups comprising 2 to 20 carbonatoms having at least one aliphatic unsaturation of Q include alkenyloxygroups such as oxybutylvinylether and alkynyloxy groups such aspropargyloxy or hexynyloxy.

Examples of halogen atoms of Q include chloro, fluoro, and bromo atoms.Examples of alkoxy groups of Q include methoxy, ethoxy, and isopropoxy.An example of an acyl group of Q is acetoxy.

Preferably, each Q is an independently selected monovalent hydrocarbongroup comprising 2 to 20 carbon atoms having at least one aliphaticunsaturation. More preferably, each Q is an independently selectedalkenyl group comprising 2 to 20 carbon atoms, with an alkenyl groupcomprising 2 to 8 carbon atoms being most preferred for Q.

In formula (II), the sum of c′+d′+e′+f′+g′+h′+i′+j′ is at least 2,preferably from 2 to 5300, more preferably from 2 to 1000. Preferably,subscript c′ is an integer from 0 to 50, with 2 to 20 being morepreferred, and 2 to 10 being most preferred. Preferably, subscript d′ isan integer from 0 to 5000, with 0 to 500 being more preferred, and 1 to300 being most preferred. Preferably, subscript e′ is an integer from 0to 48, with 0 to 30 being more preferred, and 0 to 15 being mostpreferred. Preferably, subscript f is an integer from 0 to 24, with 0 to10 being more preferred, and 0 to 6 being most preferred. Preferably,subscript g′ is an integer from 0 to 50, with 0 to 20 being morepreferred, and 0 to 10 being most preferred. Preferably, subscript h′ isan integer from 0 to 150, with 0 to 80 being more preferred, and 0 to 60being most preferred. Preferably, subscript i′ is an integer from 0 to50, with 0 to 20 being more preferred, and 0 to 10 being most preferred.Preferably, subscript j′ is an integer from 0 to 50, with 0 to 15 beingmore preferred, and 0 to 10 being most preferred.

In formula (II), n′ is an integer from 0 to 3, preferably from 2 to 3;o′ is an integer from 0 to 2, preferably from 1 to 2; p′ is an integerfrom 0 to 1, preferably 1; q′ is an integer from 0 to 1, preferably 1;r′ is an integer from 0 to 2, preferably from 1 to 2; s′ is an integerfrom 0 to 2, preferably from 1 to 2; and t′ is an integer from 0 to 3,preferably from 2 to 3.

Examples of organosilicon polymers and silicon-modified organic polymersdescribed by formula (II) include trimethylsiloxy-terminatedpolydimethylsiloxane-polymethylvinylsiloxane copolymers,vinyldimethylsiloxy-terminatedpolydimethylsiloxane-polymethylvinylsiloxane copolymers,trimethylsiloxy-terminatedpolydimethylsiloxane-polymethylhexenylsiloxane copolymers,hexenyldimethylsiloxy-terminatedpolydimethylsiloxane-polymethylhexenylsiloxane copolymers,vinyldimethylsiloxy-terminatedpolydimethylsiloxane-polymethyhexenylsiloxane copolymers,trimethylsiloxy-terminated polymethylvinylsiloxane polymers,trimethylsiloxy-terminated polymethylhexenylsiloxane polymers,vinyldimethylsiloxy-terminated polydimethylsiloxane polymers, andhexenyldimethylsiloxy-terminated polydimethylsiloxane polymers,vinyldimethylsiloxy terminatedpoly(dimethylsiloxane-monomethylsilsesquioxane) polymers,vinyldimethylsiloxy terminatedpoly(dimethylsiloxane-vinylmethylsiloxane-methylsilsesquioxane)copolymers; trimethylsiloxy terminatedpoly(dimethylsiloxane-vinylmethylsiloxane-methylsilsesquioxane)polymers, hexenyldimethylsiloxy terminatedpoly(dimethylsiloxane-monomethylsilsesquioxane) polymers,hexenyldimethylsiloxy terminatedpoly(dimethylsiloxane-hexenylmethylsiloxane-methylsilsesquioxane)copolymers; trimethylsiloxy terminatedpoly(dimethylsiloxane-hexenylmethylsiloxane-methylsilsesquioxane)polymers, vinyldimethylsiloxy terminated poly(dimethylsiloxane-silicate)copolymers, hexenyldimethylsiloxy-terminatedpoly(dimethylsiloxane-silicate) copolymers, trimethylsiloxy terminatedpoly(dimethylsiloxane-vinylmethylsiloxane-silicate) copolymers andtrimethylsiloxy terminatedpoly(dimethylsiloxane-hexenylmethylsiloxane-silicate) copolymers,vinylsiloxy or hexenylsiloxy terminatedpoly(dimethylsiloxane-hydrocarbyl copolymers), vinylsiloxy terminated orhexenylsiloxy terminated poly(dimethylsiloxane-polyoxyalkylene) blockcopolymers, alkenyloxydimethylsiloxy terminated polyisobutylene andalkenyloxydimethylsiloxy terminated polydimethylsiloxane-polyisobutyleneblock copolymers.

Examples of preferred Component (A) compounds includehexenyldimethylsiloxy-terminatedpolydimethylsiloxane-polymethylhexenylsiloxane copolymers,hexenyldimethylsiloxy-terminated polydimethylsiloxane polymers,vinyldimethylsiloxy-terminated polydimethylsiloxane polymers, vinyl orhexenyldimethylsiloxy-terminated poly(dimethylsiloxane-silicate)copolymers and vinyl or hexenyldimethylsiloxy terminatedpoly(dimethylsiloxane-hydrocarbyl) copolymers, having a degree ofpolymerization (Dp) of from 25 to 500 and a viscosity at 25° C. of from50 to 3,000 millipascal-seconds (mPa·s).

It is more preferred that Component (A) is a compound selected fromhexenyldimethylsiloxy-terminatedpolydimethylsiloxane-polymethylhexenylsiloxane copolymers,vinyldimethylsiloxy-terminated polydimethylsiloxane polymers,vinyldimethylsiloxy-terminated poly(dimethylsiloxane-silicate)copolymers each having a Dp of from 50 to 300 and a viscosity at 25° C.of from 80 to 1,000 mPa·s.

Component (A) comprises at least one compound having at least onealiphatic unsaturation. This means Component (A) may be one compoundhaving at least one aliphatic saturation or a mixture of differentcompounds. Component (A) can also have one or more aliphaticunsaturations. In preferred embodiments, component (A) comprises atleast one compound having at least two aliphatic unsaturations. Mostpreferred is when component (A) comprises one compound having at leasttwo aliphatic unsaturations

Generally, 0 to 99 parts by weight of component (A) based on totalweight percent solids (all non-solvent ingredients) is used in thecomposition. It is preferred to add 15 to 99 parts by weight ofcomponent (A) on the same basis. Component (A) compounds may be made bymethods known in the art or are commercially available.

Component (B) comprises at least one organohydrogensilicon compoundcontaining at least one silicon-bonded hydrogen atom per moleculedescribed by formula (III)

where each R is independently selected from a hydrogen atom and amonovalent hydrocarbon group comprising 1 to 20 carbon atoms which isfree from aliphatic unsaturation, a is an integer from 1 to 18, b is aninteger from 1 to 19; preferably 2 to 19, a+b is an integer from 3 to20, each X is an independently selected functional group selected from ahalogen atom, an ether group, an alkoxy group, an alkoxyether group, anacyl group, an epoxy group, an amino group, or a silyl group, or a -Z-R⁴group, where each Z is independently selected from an oxygen and adivalent hydrocarbon group comprising 2 to 20 carbon atoms, each R⁴group is independently selected from —BR_(u)Y_(2-u), —SiR_(v)Y_(3-v), ora group described by formula (IV):(Y_(3-n)R_(n)SiO_(1/2))_(c)(Y_(2-o)R_(o)SiO_(2/2))_(d)(Y_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)Y_(1-q))_(g)(CR_(r)Y_(2-r))_(h)(O(CR_(s)Y_(2-s))_(i)(CR_(t)Y_(3-t))_(j)where B refers to boron, each R is as described above, the sum ofc+d+e+f+g+h+i+j is at least 2, n is an integer from 0 to 3, o is aninteger from 0 to 2, p is an integer from 0 to 1, q is an integer from 0to 1, r is an integer from 0 to 2, s is an integer from 0 to 2, t is aninteger from 0 to 3, u is an integer from 0 to 2, v is an integer from 0to 3, each Y is an independently selected functional group selected froma halogen atom, an ether group, an alkoxy group, an alkoxyether group,an acyl group, an epoxy group, an amino group, or a silyl group, or aZ-G group, where Z is as described above, each G is a cyclosiloxanedescribed by formula (V):

where R and X are as described above, k is an integer from 0 to 18, m isan integer from 0 to 18, k+m is an integer from 2 to 20, provided informula (IV) that one of the Y groups is replaced by the Z group bondingthe R⁴ group to the cyclosiloxane of formula (III), and provided furtherif g+h+i+j>0 then c+d+e+f>0.

In formulas (III), (IV), and (V), each R group is an independentlyselected hydrogen atom or monovalent hydrocarbon group comprising 1 to20 carbon atoms free from aliphatic unsaturation. Each monovalenthydrocarbon groups of R can be linear, branched or cyclic. Eachmonovalent hydrocarbon group of R can be unsubstituted or substitutedwith halogen atoms. Examples of the monovalent hydrocarbon group of Rare as described above for R¹′. It is preferred that each R group isindependently selected from hydrogen atoms, alkyl groups comprising 1 to8 carbon atoms, or aryl groups comprising 6 to 9 carbon atoms. It ismost preferrred that each R group is independently selected fromhydrogen, methyl, alpha-methylstyryl, 3,3,3-trifluoropropyl andnonafluorobutylethyl. Each R can be identical or different, as desired.

In formulas (III) and (V), each X is an independently selectedfunctional group selected from an ether group, an alkoxy group, analkoxyether group, an acyl group, an epoxy group, an amino group, or asilyl group, or a -Z-R⁴ group.

The functional groups represented by X are selected from halogen atoms,ether groups, alkoxy groups, alkoxyether groups, acyl groups, epoxygroups, amino groups, or silyl groups. Examples of useful functionalgroups include chloro, fluoro, bromo, methoxy, ethoxy, isopropoxy, andoxybutylvinyl ether. Other useful functional groups are derived byhydrosilylation of the alkenyl group from methylvinylether,methylvinylketone, vinylacetate, vinylbenzoate, vinylacrylate,vinylstearate, vinyldecanoate, vinylmethacrylate,vinylcyclohexylepoxide, allylglycidylether,vinylcyclohexylepoxidetrimethoxysilane, trimethylvinylsilane,triethylvinylsilane, vinyltrimethoxysilane, vinyltriacetoxysilane,vinylpyridine, phenylvinylether, phenylvinylketone, and allyl aldehydewith an SiH from the siloxane precursor to formulas (III) or (V), wherethe term siloxane precursor includes the siloxane material used to makethe initial formula (III) or (V) material and any initial formula (III)material which can then be further reacted.

When X is a functional group, it is preferred that each X isindependently selected from chloro, methoxy, isopropoxy, and groupsderived by hydrosilylation of the alkenyl group from hydroxybutylvinylether, vinylcyclohexylepoxide, and allylglycidyl ether with an SiH fromthe siloxane precursor to formulas (III) or (V), where the term siloxaneprecursor includes the siloxane material used to make the initialformula (III) or (V) material and any initial formula (III) materialwhich can then be further reacted. It is more preferred that when X is afunctional group that it is derived by hydrosilylation of the alkenylgroup from allyl glycidycidyl ether with an SiH from the siloxaneprecursor to formulas (III) (ie. propylglycidyl ether).

Each X of formulas (III) and (V) may also comprise a Z-R⁴ group. It ispreferred that X is a Z-R⁴ group. It is more preferred that X includesboth -Z-R⁴ groups and functional groups derived by hydrosilylation ofallylglycidyl ether (ie. propylglycidyl ether) orvinylcyclohexylepoxide. It is most preferred that the functional groupbe derived from hydrosilylation of allylglycidyl ether (ie.propylglycidyl ether).

Each Z is independently selected from oxygen and divalent hydrocarbongroups comprising 2 to 20 carbon atoms. Examples of the divalenthydrocarbon group comprising 2 to 20 carbon atoms represented by Zinclude alkylene radicals such as methylene, ethylene, methylmethylene,propylene, isopropylene, butylene, pentylene, hexylene, andoctadecylene; alkenylene radicals such as vinylene, allylene,butenylene, and hexenylene, arylene radicals such as phenylene andxylylene; aralkylene radicals as benzylene; and alkarylene radicals suchas tolylene. Preferably, Z is a divalent hydrocarbon group comprising 2to 18 carbon atoms. It is more preferred for Z to be an alkylene group,with an alkylene group comprising 2 to 8 carbon atoms being mostpreferred.

Each R⁴ group is selected from —BR_(u)Y_(2-u), —SiR_(v)Y_(3-v), or agroup described by formula (III)(Y_(3-n)R_(n)SiO_(1/2))_(c)(Y_(2-o)R_(o)SiO_(2/2))_(d)(Y_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)Y_(1-q))_(g)(CR_(r)Y_(2-r))_(h)(O(CR_(s)Y_(2-s))_(i)(CR_(t)Y_(3-t))_(j),where R, Y, c, d, e, f, g, h, i, j, n, o, p, q, r, s, t, u, v are asdescribed above, provided in formula (IV) that one of the Y groups isreplaced by the Z group bonding the R⁴ group to the cyclosiloxane offormula (III).

In formula (III), a is an integer from 1 to 18, b is an integer from 1to 19, preferably from 2 to 19, and a+b is an integer from 3 to 20.

In formula (IV), the sum of c+d+e+f+g+h+i+j is at least 2, preferablyfrom 2 to 5300, more preferably from 2 to 1000. Preferably, subscript cis an integer from 0 to 50, with 2 to 15 being more preferred, and 2 to10 being most preferred. Preferably, subscript d is an integer from 0 to5000, with 0 to 1000 being more preferred, and 1 to 50 being mostpreferred. Preferably, subscript e is an integer from 0 to 48, with 0 to13 being more preferred, and 0 to 8 being most preferred. Preferably,subscript f is an integer from 0 to 24, with 0 to 6 being morepreferred, and 0 to 4 being most preferred. Preferably, subscript g isan integer from 0 to 50, with 0 to 20 being more preferred, and 0 to 10being most preferred. Preferably, subscript h is an integer from 0 to50, with 0 to 20 being more preferred, and 0 to 10 being most preferred.Preferably, subscript i is an integer from 0 to 50, with 0 to 20 beingmore preferred, and 0 to 10 being most preferred. Preferably, subscriptj is an integer from 0 to 50, with 0 to 15 being more preferred, and 0to 10 being most preferred.

In formula (IV), n is an integer from 0 to 3, preferably from 2 to 3; ois an integer from 0 to 2, preferably from 1 to 2; p is an integer from0 to 1, preferably 1; q is an integer from 0 to 1, preferably 1; r is aninteger from 0 to 2, preferably from 1 to 2; s is an integer from 0 to2, preferably from 1 to 2; and t is an integer from 0 to 3, preferablyfrom 2 to 3. Notwithstanding the above, since the R⁴ group as describedby formula (IV) is connected to the cyclosiloxane described by formula(III) via a Z group, one of the Y groups present in the R⁴ groupdescribed by formula (IV) will be replaced by a Z group.

In addition to a group described by formula (IV) each R⁴ group isindependently selected from —BR_(u)Y_(2-u), and —SiR_(v)Y_(3-v) where Brefers to boron, u is an integer from 0 to 2, preferably from 1 to 2 andv is an integer from 0 to 3, preferably from 2 to 3. Examples of theseR⁴ groups are derived from borane or silanes, such as for example,trivinylborane, diallyldimethylsilane, divinyldimethylsilane andvinyltrimethylsilane.

Each Y of R⁴ is an independently selected functional group selected froma halogen atom, an ether group, an alkoxy group, an alkoxyether group,an acyl group, an epoxy group, an amino group, or a silyl group, or a-Z-G group. The functional groups are exemplified as described above forX. The Z group is also as described above.

Each G is a cyclosiloxane described by formula (V):

where R and X are as described above, k is an integer from 0 to 18, m isan integer from 0 to 18, and k+m is an integer from 2 to 20.

In formula (V), each k is an integer from 0 to 18, preferably from 1 to3.

In formula (V), each m is an integer from 0 to 18, preferably from 1 to10, most preferably from 2 to 4.

The sum of k+m is an integer from 2 to 20, preferably from 2 to 6, mostpreferably from 2 to 5.

The Y group of formula (IV) is preferably a -Z-G group. Although it isnot required for there to be any -Z-G groups in theorganohydrogensilicon compound of the present invention, it is preferredthat on average the organohydrogensilicon compounds contain at least 1-Z-G group with at least 2 -Z-G groups being more preferred.

The R⁴ group described by formula (IV) can be linear, cyclic, branchedor resinous. The R⁴ group described by formula (IV) can be a siloxanematerial where the polymer chain units contain only siloxane units, orit can be a mixture of siloxane units with hydrocarbon units oroxyhydrocarbon units, where oxyhydrocarbon refers to a hydrocarbon groupwhich also includes at least one oxygen atom. It is preferred that theR⁴ group is a siloxane material, and more preferred that R⁴ is a linearsiloxane material.

Examples of preferred R⁴ groups described by formula (IV) useful in theinvention include —R₂SiO(R₂SiO)_(d)SiR₂-Z-G, —R₂SiOSiR₃, —R₂SiOSiR₂—Y,—RSi(OSiR₃)₂, where d is an integer from 1 to 50 and Z, G, and R are asdescribed above. More preferred R⁴ groups are as described above when Ris methyl, and d is an average of 8.

With respect to the organohydrogensilicon compounds useful in thepresent invention it is preferred that if g+h+i+j>0 then c+d+e+f>0. Itis more preferred that (a) at least one X group of Formula (III) is a-Z-R⁴ group (b) if Z is a divalent hydrocarbon group, a=1, c=2,e+f+g+h+i+j=0 and d>0, then at least one d unit (ie.Y_(2-o)R_(o)SiO_(2/2)) contain a -Z-G group or the c units (ie.Y_(3-n)R_(n)SiO_(1/2)) have no -Z-G group or at least two -Z-G groups,and (c) if Z is a divalent hydrocarbon group, a=, c=2 andd+e+f+g+h+i+j=0, then the c units (ie. Y_(3-n)R_(n)SiO_(1/2)) have no-Z-G group or at least two -Z-G groups.

It is also preferred that the organohydrogensilicon compounds useful inthe present invention have a viscosity from 5 to 50,000 mPa·s, morepreferred from 10 to 10,000 mPa·s and most preferred from 25 to 2,000mPa·s.

The organohydrogensilicon compounds contain at least one silicon-bondedhydrogen atom per molecule. Preferably, the organohydrogensiliconcompounds contain at least 2 silicon-bonded hydrogen atoms per molecule.It is most preferred that the organohydrogensilicon compounds contain atleast 3 silicon-bonded hydrogen atoms per molecule.

Examples of the types of organohydrogensilicon compounds described byformula (III) useful in the present composition are as follows where Meis methyl, d (which equals d₁+d₂) is as described above, and x can rangefrom 1 to 100; preferably 1 to 20.

Other example include the compounds described above where certain of theSiH bonds are replaced with such other groups, more preferably 5 to 50%,most preferably 10 to 30%

Examples of the hydrocarbon, oxyhydrocarbon and functional groupsdescribed above include the described later in this specification forgroup A. Preferred groups include functional groups derived byhydrosilylation of allylglycidyl ether (ie. propylglycidyl ether) orvinylcyclohexylepoxide, alkyl groups such as 1-hexyl, 1-octyl, andethylcyclohexene and alkcenyl groups such as 5-hexenyl. It is mostpreferred that the SiH bonds are replaced by functional groups derivedby hydrosilylation of allylglycidyl ether.

The most preferred organohydrogensilicon compounds described by formula(III) include the compound described below where Me is methyl, d is anaverage of 8 and x is an integer from 1 to 15 and the compound describedbelow when 10 to 30% of the SiH bonds are replaced by functional groupsderived by hydrosilylation of allylglycidyl ether.

The amounts of component (A) and component (B) used to prepare thepresent composition will depend on the individual components and thedesired SiH to aliphatic unsaturation ratio. The ratio of SiH incomponent (B) to aliphatic unsaturation from component (A) useful toprepare the compositions of the present invention can be from 0.5:1 to4:1. It is preferred that a SiH to aliphatic unsaturation ratio of 1:1to 3.5:1 be used with a ratio of 1.5:1 to 3:1 being most preferred. Ifcomponents (A) and (B) are not the only materials containing aliphaticunsaturated groups and SiH-containing groups in the present composition,then the above ratios relate to the total amount of such groups presentin the composition rather than only those components.

Component (C) comprises any catalyst typically employed forhydrosilylation reactions. It is preferred to use platinum groupmetal-conining catalysts. By platinum group it is meant ruthenium,rhodium, palladium, osmium, iridium and platinum and complexes thereof.Platinum group metal-containing catalysts useful in preparing thecompositions of the present invention are the platinum complexesprepared as described by Willing, U.S. Pat. No. 3,419,593, and Brown etal, U.S. Pat. No. 5,175,325, each of which is hereby incorporated byreference to show such complexes and their preparation. Other examplesof useful platinum group metal-containing catalysts can be found in Leeet al., U.S. Pat. No. 3,989,668; Chang et al., U.S. Pat. No. 5,036,117;Ashby, U.S. Pat. No. 3,159,601; Lamoreaux, U.S. Pat. No. 3,220,972;Chalk et al., U.S. Pat. No. 3,296,291; Modic, U.S. Pat. No. 3,516,946;Karstedt, U.S. Pat. No. 3,814,730; and Chandra et al., U.S. Pat. No.3,928,629 all of which are hereby incorporated by reference to showuseful platinum group metal-containing catalysts and methods for theirpreparation. The platinum-containing catalyst can be platinum metal,platinum metal deposited on a carrier such as silica gel or powderedcharcoal, or a compound or complex of a platinum group metal. Preferredplatinum-containing catalysts include chloroplatinic acid, either inhexahydrate form or anhydrous form, and or a platinum-containingcatalyst which is obtained by a method comprising reactingchloroplatinic acid with an aliphatically unsaturated organosiliconcompound such as divinyltetramethyldisiloxane, or alkene-platinum-silylcomplexes as described in U.S. patent application Ser. No. 10/017,229,filed Dec. 7, 2001, such as (COD)Pt(SiMeCl₂)₂, where COD is1,5-cyclooctadiene and Me is methyl. These alkene-platinum-silylcomplexes may be prepared, for example by mixing 0.015 mole (COD)PtCl₂with 0.045 mole COD and 0.0612 moles HMeSiCl₂.

The appropriate amount of the catalyst will depend upon the particularcatalyst used. The platinum catalyst should be present in an amountsufficient to provide at least 2 parts per million (ppm), preferably 5to 200 ppm of platinum based on total weight percent solids (allnon-solvent ingredients) in the composition. It is highly preferred thatthe platinum is present in an amount sufficient to provide 5 to 150weight ppm of platinum on the same basis. The catalyst may be added as asingle species or as a mixture of two or more different species. Addingthe catalyst as a single species is preferred.

The compositions of the present invention may also comprise an inhibitor(D). This optional component (D) can be any material that is known tobe, or can be, used to inhibit the catalytic activity of platinum groupmetal-containing catalysts. As used herein, the term “inhibitor” means amaterial that retards activity of a catalyst at room temperature butdoes not interfere with the properties of the catalyst at elevatedtemperatures. Examples of suitable inhibitors include ethylenically oraromatically unsaturated amides, acetylenic compounds, silylatedacetylenic compounds, ethylenically unsaturated isocyanates, olefinicsiloxanes, unsaturated hydrocarbon monoesters and diesters, conjugatedene-ynes, hydroperoxides, nitriles, and diaziridines.

Preferred inhibitors include acetylenic alcohols exemplified by1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol,2-ethynyl-isopropanol, 2-ethynyl-butane-2-ol, and3,5-dimethyl-1-hexyn-3-ol, silylated acetylenic alcohols exemplified bytrimethyl (3,5-dimethyl-1-hexyn-3-oxy)silane,dimethyl-bis-(3-methyl-1-butyn-oxy)silane,methylvinylbis(3-methyl-1-butyn-3-oxy)silane, and((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, unsaturated carboxylicesters exemplified by diallyl maleate, dimethyl maleate, diethylfumarate, diallyl fumarate, and bis-2-methoxy-1-methylethylmaleate,mono-octylmaleate, mono-isooctylmaleate, mono-allyl maleate, mono-methylmaleate, mono-ethyl fumarate, mono-allyl fumarate, and2-methoxy-1-methylethylmaaleate; conjugated ene-ynes exemplified by2-isobutyl-1-butene-3-yne, 3,5-dimethyl-3-hexene-1-yne,3-methyl-3-pentene-1-yne, 3-methyl-3-hexene-1-yne, 1-ethynylcyclohexene,3-ethyl-3-butene-1-yne, and 3-phenyl-3-butene-1-yne, vinylcyclosiloxanessuch as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and amixture of a conjugated ene-yne as described above and avinylcyclosiloxane as described above.

Most preferred inhibitos are diallyl maleate,bis-2-methoxy-1-methylethylmaleate, 1-ethynyl-1-cyclohexanol, and3,5-dimethyl-1-hexyn-3-ol.

When used, it is preferred that from 0.03 to 10 parts by weight ofinhibitor be used based on total weight percent solids (all non-solventingredients) in the composition. It is most preferred that 0.03 to 2parts by weight of inhibitor be used on the same basis.

Although the use of Component (B) improves the bath life ofcompositions, sometimes it may be desirable to extend the bath life foran even longer period of time. As used herein, “bath life” means thetime it takes a fully formulated coating composition to double inviscosity at 40° C. Therefore, a further optional ingredient of thepresent composition is a bath life extender (E) which may be added in atotal amount sufficient to further retard the curing reaction at roomtemperature. Examples of suitable bath life extenders include compoundswhich contain one or more primary or secondary alcohol groups,carboxylic acids (including compounds which yield carboxylic acids whenexposed to water at room temperature), cyclic ethers, and water.Included in this group are the primary and secondary alcohols; diols andtriols, such as ethylene glycol, propylene glycol and glycerine; partialethers of diols and triols, such as 2-methoxyethanol, 2-methoxypropanol,and 2-methoxyisopropanol; tetrahydrofuran; water and aqueous solutionsof mineral acids, alkalis, and salts. Primary and secondary alcohols,preferably having fewer than 10 carbon atoms are the most preferred forthe compositions of this invention. Examples include methanol,1-butanol, 2-butanol, tetradecanol and other alkanols, such as ethanol,and normal-, and iso-propanol, iso-butanol, and the normal-, secondary-,and iso-pentanols, -hexanols, -heptanols, and -octanols; benzyl alcohol,phenol, and other aromatic alcohols such as methylphenyl carbinol, and2-phenylethyl alcohol; allyl alcohol, and cyclohexanol. It is highlypreferred that the bath life extender is benzyl alcohol or water.

When included in the present composition, it is preferred that from0.005 to 10 parts by weight bath life extender (E) based on total weightpercent solids (all non-solvent ingredients) in the composition be used.More preferably, the amount of bath life extender to be used fallswithin the range of 0.005 to 5 parts on the same basis, and mostpreferably 0.005 to 1 part by weight based on total weight percentsolids (all non-solvent ingredients) in the composition.

The compositions of the present invention may also optionally comprise(F) a release additive. Any of the well-known release additives in theart may be employed. Generally, the release additive comprises asilicone resin and may include at least one additional componentselected from the following components: (i) an alkenylatedpolydiorganosiloxane, (ii) one or more primary alkenes containing from14 to 30 carbon atoms, and (iii) one or more branched alkenes containingat least 10 carbon atoms.

The siloxane resin consists essentially of R² ₃SiO_(1/2) units (alsoknown as M units) and SiO_(4/2) units (also known as Q units) where eachR² is independently selected from hydrogen, a monovalent hydrocarbongroup comprising 1 to 20 carbon atoms free of aliphatic unsaturation ora monovalent hydrocarbon group comprising 2 to 20 carbon atoms havingaliphatic unsaturation.

Examples of the monovalent hydrocarbon groups free of aliphaticunsaturation of R² are as described above for such groups of R. Examplesof the monovalent hydrocarbon groups having at least one aliphaticunsaturation of R² are as described later in the specification for suchgroups of A. Preferably each R² is independently selected from amonovalent hydrocarbon group comprising 1 to 20 carbon atoms free ofaliphatic unsaturation or a monovalent hydrocarbon group comprising 2 to20 carbon atoms having at least one aliphatic unsaturation. The molarratio of R³ ₃SiO_(1/2) units to SiO_(4/2) is from 0.6:1 to 4:1,preferably from 0.6:1 to 1.9:1, and most preferably from 0.7:1 to 1.6:1.

The release additive may also comprise one or more of (i) an alkenylatedpolydiorganosiloxane, (ii) one or more primary alkenes containing from14 to 30 carbon atoms, or iii) one or more branched alkenes containingat least 10 carbon atoms.

Preferred alkenylated polydiorganosiloxanes (i) include those describedlater in the specification for component (A). Each primary alkene (ii)used may be any primary alkene containing from 10 to 30 carbon atomssuch as, for example, tetradecene and octadecene. Each branched alkene(iii) used may be any one or more suitable branched alkenes where thetotal number of carbons is at least 10 and preferably at least 20.

The release modifier generally comprises from 5 to 85 weight percent andpreferably from 25 to 85 weight percent of the siloxane resin, theremainder being made up of one or more of components (i), (ii), or(iii).

Although optional, when used in a coating composition, it is preferredthat 5 to 99 parts by weight of the release modifier be added based ontotal weight percent solids (all non-solvent ingredients) in thecomposition.

The compositions of the present invention can further comprise otheroptional components commonly used in platinum group metal catalyzedorganosilicon compositions, such as reinforcing and extending fillers,mist reducing additives, anchorage additives, hydrocarbon andhalohydrocarbon solvents, colorants, stabilizers, and adhesive-releasemodifiers such as non-functional fluids or gums.

The compositions of this invention may also contain up to 99 parts byweight of a solvent, however, it is preferred that the solvent, ifemployed, range from 70 to 90 parts by weight, said weight being basedon total weight percent solids (all non-solvent ingredients) in thecomposition. Examples of useful solvents include toluene, xylene,methylisobutylketone, isopropanol, and heptane.

A preferred embodiment of the present invention is a curable coatingcomposition. These compositions may be applied out of solvent or as anoil in water emulsion.

Components (A), (C), and optional components (D)-(F) are commerciallyavailable or can be made by methods known in the art. Theorganohydrogensilicon compounds (component (B)) described by Formula(III) can be made in a straightforward manner, for example via aplatinum catalyzed coupling of methylhydrogencyclosiloxanes with areactant containing aliphatic unsaturation, hydroxy functionalities or amixture of both. The desired product is a function not only of thereactants but also of the reaction stoichiometry. The reaction can beconducted by premixing the reactants followed by catalysis or by usingone of the reactants as a controlling reagent. Once an initialorganohydrogensilicon compound is prepared, subsequent hydrosilylationsor condensations may also be done to replace or convert some of theremaining SiH bonds to other types of groups. After the desiredorganohydrogensilicon compound is made it is preferred to deactivate thecatalyst using an inhibitor.

Generally, the ratio of SiH to aliphatic unsaturation or SiH to hydroxyfunctionality useful to prepare the organohydrogensilicon compounds ofcomponent (B) of the present composition is at least 2.5:1. It ispreferred that a ratio of SiH to aliphatic unsaturation ratio or SiH tohydroxy functionality of 20:1 to 2.5:1 be used with a ratio of 4:1 to3:1 being most preferred. Notwithstanding the above, iforganohydrogensilicon compounds described by formula (III) which areprepared using the above ratios are then further hydrosilylated orcondensed, for example to convert or replace some of the remaining SiHgroups and form other organohydrogensilicon compounds described byformula (III), the ratio of SiH to aliphatic unsaturation or SiH tohydroxy functionality to be used for these subsequent reactions need notfollow the above recommendations but rather is limited only by theamount of SiH which is desired on such final organohydrogensiliconcompound.

In one method, the organohydrogensilicon compounds having at least onesilicon-bonded hydrogen are prepared by (1) mixing (A1) at least oneorganohydrogen cyclosiloxane comprising at least 2 SiH bonds permolecule and having the formula

with (B1) at least one compound comprising at least one aliphaticunsaturation or at least one hydroxy group per molecule described byBR_(u)A_(3-u), SiR_(v)A_(4-v), or a group described by formula(A_(3-n)R_(n)SiO_(1/2))_(c)(A_(2-o)R_(o)SiO_(2/2))_(d)(A_(1-p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)A_(1-q))_(g)(CR_(r)A_(2-r))_(h)(O(CR_(s)A_(2-s))_(i)(CR_(t)A_(3-t))_(j)so that ratio of SiH bonds in component (A1) to the aliphaticunsaturation or hydroxy group of component (B1) is at least 2.5:1; (2)effecting a reaction between components (A1) and (B1) in the presence of(C1) a catalyst to form a reaction mixture comprisingorganohydrogensilicon compounds having at least one SiH bond permolecule; (3) optionally, adding an inhibitor to the reaction mixture;and (4) optionally, isolating the organohydrogen silicon compounds;where B is boron, X, R, a, b, c, d, e, f, g, h, i, j, n, o, p, q, r, s,t, u, v are as defined above, and each A is independently selected froma hydroxy group, a monovalent hydrocarbon group comprising at least onealiphatic unsaturation and 2 to about 20 carbon atoms, a monovalentoxyhydrocarbon group comprising at least one aliphatic unsaturation and2 to about 20 carbon atoms, or a functional group selected from ahalogen atom, an ether group, an alkoxy group, an alkoxyether group, anacyl group, an epoxy group, an amino group, or a silyl group, providedat least one A group has an aliphatic unsaturation or a hydroxy group.

In another method, the organohydrogensilicon compounds having at leastone silicon-bonded hydrogen are prepared by (1′) mixing (A1) at leastone organohydrogen cyclosiloxane comprising at least 2 SiH bonds permolecule and having the formula_(,)

with (C1) a catalyst to form a SiH premix; (2′) effecting a reaction byadding to the SiH premix (B1) at least one compound comprising at leastone aliphatic unsaturation or at least one hydroxy group per moleculedescribed by BR_(u)A_(3-u), SiR_(v)A_(4-v), or a group described byformula(A_(3-n)R_(n)SiO_(1/2))_(c)(A_(2-o)R_(o)SiO_(2/2))_(d)(A_(1-p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)A_(1-q))_(g)(CR_(r)A_(2-r))_(h)(O(CR_(s)A_(2-s))_(i)(CR_(t)A_(3-t))_(j)so that ratio of SiH bonds in component (A1) to the aliphaticunsaturation or hydroxy group of component (B1) is at least 2.5 to forma reaction mixture comprising organohydrogen silicon compounds having atleast one SiH bond per molecule; (3′) optionally, adding an inhibitor tothe reaction mixture; and (4′) optionally, isolating the organohydrogensilicon compounds; where B is boron, and A, X, R, a, b, c, d, e, f, g,h, i, j, n, o, p, q, r, s, t, u, and v are as defined above.

In another method, the organohydrogensilicon compounds having at leastone silicon-bonded hydrogen are prepared by (1″) mixing (B1) at leastone compound comprising at least one aliphatic unsaturation or at leastone hydroxy group per molecule described by BR_(u)A_(3-u),SiR_(v)A_(4-v), or a group described by formula(A_(3-n)R_(n)SiO_(1/2))_(c)(A_(2-o)R_(o)SiO_(2/2))_(d)(A_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)A_(1-q))_(g)(CR_(r)A_(2-r))_(h)(O(CR_(s)A_(2-s))_(I)(CR_(t)A_(3-t))_(j),with (C1) a catalyst to form a aliphatic unsaturation premix or hydroxypremix respectively; (2″) effecting a reaction by adding the aliphaticunsaturation premix or hydroxy premix to (A1) at least oneorganohydrogen cyclosiloxane comprising at least 2 SiH bonds permolecule and having the formula

so that ratio of SiH bonds in component (A1) to the aliphaticunsaturation or hydroxy group of component (B1) is at least 2.5 to forma reaction mixture comprising organohydrogen silicon compounds having atleast one SiH bond per molecule (3″) optionally, adding an inhibitor tothe reaction mixture; and (4″) optionally, isolating the organohydrogensilicon compounds; where B is boron, and A, X, R, a, b, c, d, e, f, g,h, i, j, n, o, p, q, r, s, t, u, and v are as defined above.

Each A group may be independently selected from functional groupsselected from a halogen atom, an ether group, an alkoxy group, analkoxyether group, an acyl group, an epoxy group, an amino group, or asilyl group. Examples of such functional groups represented by A are asdescribed above for X.

Each A group may also be independently selected from hydroxy groups,monovalent hydrocarbon groups comprising 2 to 20 carbon atoms havingaliphatic unsaturation and monovalent oxyhydrocarbon groups comprising 2to 20 carbon atoms having aliphatic saturation. The aliphaticunsaturations of A can be found in a pendant position to the hydrocarbonchain, at the end of the hydrocarbon chain, or both, with the terminalposition being preferred. Each monovalent hydrocarbon group andoxyhydrocarbon group of A can be linear, branched or cyclic and may beunsubstituted or substituted with halogen atoms. Examples of monovalenthydrocarbon groups comprising 2 to 20 carbon atoms having aliphaticunsaturation include alkenyl groups such as vinyl, allyl, 3-butenyl,4-pentenyl, 5-hexenyl, cyclohexenyl, 6-heptenyl, 7-octenyl, 8-nonenyl,9-decenyl, 10-undecenyl, and diene groups comprising 4 to 20 carbonatoms such as 4,7-octadienyl, 5,8-nonadienyl, 5,9-decadienyl,6,11-dodecadienyl, 4,8-nonadienyl, and 7,13-tetradecadienyl. Examples ofmonovalent oxyhydrocarbon groups comprising 2 to 20 carbon atoms includealkenyloxy groups such as oxybutylvinylether and alkynyloxy groups suchas propargyloxy or hexynyloxy.

Preferably, each A is independently selected from a monovalenthydrocarbon group comprising 2 to 20 carbon atoms having at least onealiphatic unsaturation, a hydroxy group, or an epoxy group. It is morepreferred for each A to be an independently selected alkenyl groupcomprising 2 to 20 carbon atoms, with an alkenyl group comprising 2 to 8carbon atoms being most preferred for A.

The methods described above for making organohydrogensilicon compoundshaving at least one SiH group per molecule, are examples of somepreferred methods and are not meant to describe all the various methodsof making such materials. Depending on the starting materials used andthe desired organohydrogensilicon compound, the initialorganohydrogensilicon compound formed may be subjected to subsequenthydrosilylations and/or condensations utilizing at least onehydrocarbon, oxyhydrocarbon or functional compound having at least onealiphatic unsaturation or hydroxy group so to form the desiredorganohydrogensilicon compound having at least one SiH group permolecule as described by Formula (III).

The methods described above preferably further comprise step (2a), (2′a)or (2″a) adding at least one hydrocarbon, oxyhydrocarbon or functionalcompound having at least one aliphatic unsaturation or hydroxy group tothe reaction mixture comprising organohydrogensilicon compounds havingat least one SiH bond per molecule formed in step (2), (2′), or (2″)respectively so to form a second reaction mixture comprisingorganohydrogensilicon compounds having at least one SiH bond permolecule where a certain percentage of SiH groups have been converted tohydrocarbon, oxyhydrocarbon or functional groups.

Examples of the hydrocarbon, oxyhydrocarbon and functional compoundshaving at least one aliphatic unsaturation or hydroxy group useful forthese subsequent reactions include compounds which contain the type ofgroups described above for A so long as they also include either aaliphatic unsaturation or hydroxy group. Preferred compounds includefunctional compounds such as allylglycidyl ether andvinylcyclohexylepoxide, alkenes such as 1-hexene, 1-octene, andvinylcyclohexene, and dienes such as 1,5-hexadiene.

When these subsequent reactions are utilized it is preferred that 5 to70% of the SiH groups are replaced or converted to hydrocarbon,oxyhydrocarbon or functional groups, more preferably 5 to 50% and mostpreferably 10 to 30%.

The compounds containing at least one aliphatic unsaturation or hydroxygroup (component (B1)) and the organohydrogen cyclic siloxanes(component (A1)) used to make the organohydrogensilicon compounds(component (B)) may be prepared by known methods or are commerciallyavailable. It is preferred that the organohydrogen cyclic siloxanes usedin the reaction are relatively pure and substantially free fromoligomeric linears.

The catalysts (component (C1)) useful to make the organohydrogensiliconcompounds are those catalysts typically employed for hydrosilylationand/or condensation reactions. It is preferred to use platinum groupmetal-containing catalysts. By platinum group it is meant ruthenium,rhodium, palladium, osmium, iridium and platinum and complexes thereof.Examples of these catalysts and useful amounts are the same as describedabove for component (C) when making the composition of the presentinvention.

After the desired organohydrogensilicon compound having at least one SiHbond is prepared, an additional preferred step is to deactivate thecatalyst using an inhibitor. The inhibitors useful for this are thosewell known in the art and described above for Component (D) of thepresent invention. The optimal level of inhibitor used for deactivationwill vary for each inhibitor. Generally, a level of 0.2 to 1 parts byweight based on total weight percent solids (all non-solventingredients) is desired.

The temperature of the reaction is not strictly specified, but generallyfalls within the range of about 20° to 150° C. The length of reactiontime is also not critical, and is generally determined by the additionrate of controlling reagent.

Optionally, the reaction can be run using common solvents such astoluene, xylene, methylisobutylketone, and heptane.

Once the platinum catalyst has been deactivated, routine volatilestripping procedures can be used to remove unreacted polyorganohydrogencyclic siloxanes and any solvent that may have been used.

The compositions of the present invention can be prepared byhomogeneously mixing components (A), (B), and (C), and any optionalcomponents in any order using any suitable mixing means, such as aspatula, a drum roller, a mechanical stirrer, a three roll mill, a sigmablade mixer, a bread dough mixer, and a two roll mill. The presentcompositions can be supplied in any desired package combinationincluding multi-component to single component packages. It is preferredthat component (C), the platinum group metal-containing catalyst, bebrought together in the presence of components (A), (B), (D), and anyother optional components.

In other preferred embodiments, this invention relates to a method ofmaking a cured coating and the cured coating, the method comprising thesteps of (I) mixing: (A) at least one compound having at least twoaliphatic unsaturation; (B) at least one organohydrogensilicon compoundcontaining at least three silicon-bonded hydrogen atom per molecule and(C) a platinum group metal-containing catalyst which is present in anamount sufficient to catalyze the reaction (II) coating the mixture from(I) on the surface of a substrate; and (III) exposing the coating andthe substrate to an energy source selected from (i) heat and (ii)actinic radiation in an amount sufficient to cure the coating. Thismethod can further comprise applying a pressure sensitive adhesive onthe coating after step (III). Components (A), (B) and (C) are asdescribed above including preferred embodiments and amounts thereof.

By actinic radiation it is meant ultraviolet light; electron beamradiation; and alpha-, beta-, gamma- and x-rays. By heat it is meantinfrared radiation, hot air, microwave radiation, etc. Of course actinicradiation is frequently accompanied by heat and the use of a combinationof the two falls within the scope and spirit of the present method. Inaddition preferred method, the coating process can be accomplished byany suitable manner known in the art, such as by spreading, brushing,extruding, spraying, gravure, kiss-roll and air-knife.

In a preferred embodiment of the instant method, the solid substrate isa flexible sheet material such as paper, polyolefin film andpolyolefin-coated paper or foil. Other suitable solid substrates thatcan be coated by the process of this invention include other cellulosicmaterials such as wood, cardboard and cotton; metallic materials such asaluminum, copper, steel and silver; siliceous materials such as glassand stone; and synthetic polymer materials such as polyolefins,polyamides, polyesters and polyacrylates. As to form, the solidsubstrate can be substantially sheet-like, such as a peelable releaseliner for pressure sensitive adhesive; a fabric or a foil; orsubstantially three-dimensional in form.

After the silicone coating composition has been coated onto a substrateit is heated and/or irradiated with actinic radiation, as noted herein,to cure the liquid coating and to adhere it to the substrate.

In a preferred embodiment of the coating method of this invention, aflexible sheet material, such as paper, polyolefin film andpolyolefin-coated paper or foil, is coated with a thin coating of thesilicone coating composition, preferably in a continuous manner and thethus-coated material is then heated and/or irradiated to rapidly curethe coating, to provide a sheetlike material bearing on at least onesurface thereof an adhesive-releasing coating. The adhesive-releasingcoating is subsequently brought into contact with a pressure sensitiveadhesive, preferably in an in-line manner, to form an article having apeelable, i.e. releasable, adhesive/coating interface. Examples of suchan article include, adhesive labels having a peelable backing, adhesivetape in roll form and adhesive packaged in a strippable container. Thepressure sensitive adhesive can be non-silicon-based, such as thewell-known acrylic or rubber types or silicon-based, such as theperoxide- or platinum-curable polydiorganosiloxane-based adhesives.

This method is also applicable to adhesive materials, other thanpressure sensitive adhesives. Examples of said adhesive materialsinclude foods, graphite composites, asphalt and gum polymers.

In addition to being useful for making coatings, the presentcompositions are also useful for making elastomers, adhesives, foams orfluids.

The following examples are disclosed to further teach, but not limit,the invention, which is properly delineated by the appended claims.

Test Methods

Gas Chromatography (GC)—GC data was collected on an HP5890A equippedwith an FID and a J&W Scientific 30 m by 0.25 mm i.d. DB-1 column with0.25 micron film thickness.

Gel Permeation Chromatography (GPC)—GPC data was collected using aWaters 515 pump, a Water 717 autosampler and a Waters 2410 differentialrefractometer. The separation was made with two (300 mm×7.5 mm) PolymerLaboratories Plgel 5 um Mixed-C columns, preceded by a Plgel 5 um guardcolumn. HPLC grade toluene eluent was used at 1.0 mL/min flowrate andcolumns and detector were heated to 45° C. An injection volume of 50 uLwas used and the sample prefiltered through a 0.45 um PTFE syringefilter. Molecular weight averages were determined relative to acalibration curve (4^(th) order) created using polydimethylsiloxane(PDMS) standards covering the molecular weight range of 1300-850,000.

Silicon 29 Nuclear Magnetic Spectroscopy (²⁹Si NMR) ²⁹Si NMR data wascollected on a Varian Mercury 300 using chloroform D solvent. Theexperiment was conducted with a relaxation delay of 60 sec with a gateddecoupled pulse sequence using a 5 mm switchable PFG probe was used.Alternatively, the sample was run on a Mercury 400 using a Nalorac 16 mmsilicon free Pulsetune® probe with 0.03 M Cr(acac)₃ as a relaxationreagent and gated decoupling to ensure quantitative conditions. Bothused 90 degree pulsewidth and the 400 used a 12 sec relaxation delay.

SiH Measurement—The material was measured out (according to estimatedSiH content) in 125 mL Erlenmeyer flask to nearest 0.01 grams and sampleweight recorded. To this was added 20 mL of prepared mercuric acetatesolution (4% mercury acetate powder, 96% (1:1 mixture)methanol/chloroform), the flask was then covered and swirled to mix. Ablank sample (no SiH containing material added) was also prepared forcomparision. After samples stood for 30 minutes, they were quenched with20 mL of prepared calcium chloride solution (25% calcium chloride, 75%methanol). Then 10 drops of prepared phenolphthalein solution (1%phenolphthalein in ethanol) from small pipet was added. The samples werethen titrated with 0.1N methanolic potassium hydroxide and measurementstaken.

Bath life Measurement—Viscosity was measured on a Brookfield DV-II+spindle viscometer or DV-II cone and plate viscometer using theappropriate spindle and spindle speed for the viscosity range of theformulation being measured. Bath life is defined as the time it takes afully formulated coating composition to double in viscosity at 40° C.

Measurement of Cure—To measure cure based on percent extractablesilicone, a sample of silicone coated substrate was taken in the form ofa circular disk. After obtaining an initial coat weight measurement onthe sample by X-ray fluorescence (XRF) on an Oxford Lab-X 3000 BenchtopXRF Analyzer, it was submerged in methylisobutyl ketone (MIBK), withagitation, for 30 minutes. After MIBK extraction, the sample was removedfrom the MIBK solvent, allowed to air dry and a second coat weightmeasurement acquired. The percent extractable silicone is defined as thepercent loss in silicone coat weight.

Preparation of Organohydrogensilicon Compounds

EXAMPLE 1

To a reaction vessel was added 2947 g of a poly(methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (49.1 molesSiH) and 5053 g of a dimethylvinylsiloxy end-blockedpolydimethylsiloxane polymer having an average Dp of about 8 (14.4 molesvinyl) to give an SiH/SiVi ratio of 3.4:1. The polymers were well mixedand a vinylsiloxane diluted platinum (Pt) catalyst added to give a Ptcontent of about 12 ppm. An exothermic reaction was initiated and over aperiod of 10 minutes the temperature of the vessel contents rose from25° C. to 137° C. After cooling for 2 hours,bis(2-methoxy-1-methylethyl)maleate (80 g, 1 wt %) was added tostabilize the Pt from further activity. The resulting polymer was notstripped and was shown by GC to have a remaining unreacted MeH cyclicscontent of about 4%. The isolated product had a viscosity of 78 mPa·s, aSiH level of 0.42 wt % (SiH as H) as determined by titration and a GPCMn 2810 and Mw=8115 vs polydimethylsiloxane (PDMS) standards. ²⁹Si NMRanalysis of the product demonstrated that all vinyl functionality hasbeen consumed yielding silethylene bridges, no ring opening has occurredand that the resulting molecular structure is consistent with amethylhydrogen cyclic siloxane capped linear siloxane polymer asdescribed below, where Me is methyl, x is an average of 6.5 for Mw andan average of 1.5 for Mn and d is an average of about 8.

EXAMPLE 2

To a reaction vessel was added 5211 g of a poly(methylhydrogen) cyclicsiloxane (MeH cyclics) having an average degree of polymerization (Dp)of about 4.4 (86.7 moles SiH) and 3340 g of a dimethylvinylsiloxyend-blocked polydimethylsiloxane having an average Dp of about 8 (9.6moles vinyl) to give an SiH/SiVi ratio of 9:1. The polymers were wellmixed and a vinylsiloxane diluted platinum (Pt) catalyst added to give aPt content of about 12 ppm. An exothermic reaction was initiated andover a period of 10 minutes the temperature of the vessel contents rosefrom 23° C. to 100° C. After cooling for 30 minutes,bis(2-methoxy-1-methylethyl)maleate (60 g, 0.7 wt %) was added tostabilize the Pt from further activity. The resulting product wasstripped on a roto-vap at 1 mm Hg and 50° C. to remove unreactedpoly(methylhydrogen) cyclic siloxane. The isolated product had aviscosity of 23 mPa·s, a SiH level of 0.58 wt % (SiH as H) as determinedby titration and a GPC Mn=1396 and Mw=2753 vs PDMS standards. ²⁹Si NMRanalysis of the crosslinker product demonstrated that all vinylfunctionality has been consumed yielding silethylene bridges, no ringopening has occurred and that the resulting molecular structure isconsistent with a methylhydrogen cyclic siloxane capped linear siloxanepolymer, where Me is methyl, x is an average of 1.5 for Mw and averageof 0 for Mn, and d is an average of about 8.

EXAMPLE 3

To a reaction vessel was added 11.1 g of a poly(methylhydrogen)cyclosiloxane having an average Dp of about 4.4 and 50 g of adimethylvinylsiloxy end-blocked polydimethylsiloxane polymer having anaverage Dp of about 25 to give an SiH/SiVi ratio of 3.5:1. The polymerswere well mixed and a vinylsiloxane diluted Pt catalyst added to give aPt content of about 10 ppm. The typical and expected exothermic reactionwas observed. The resulting product was not stripped and was usedimmediately for performance evaluation without the Pt being deactivated.Titration showed that the product had an SiH level of 0.20 wt % (SiH asH). ²⁹Si NMR analysis of the product would demonstrate that all vinylfunctionality has been consumed yielding silethylene bridges, no ringopening has occurred and that the resulting molecular structure isconsistent with a methylhydrogen cyclic siloxane capped linear siloxanepolymer as described below, where Me is methyl, x is an average of 6.5for Mw and an average of 1.5 for Mn and d is an average of about 8.

EXAMPLE 4

To a reaction vessel was added 312 g of a poly(methylhydrogen)cyclosiloxane having an average Dp of about 4.4 (5.2 mol SiH) and 3000 gof a dimethylvinylsiloxy end-blocked polydimethylsiloxane polymer havingan average Dp of about 60 (1.5 mol Vi) to give an SiH/SiVi ratio of3.5:1. The polymers were well mixed and a vinylsiloxane diluted Ptcatalyst added to give a Pt content of about 10 ppm. The typical andexpected exothermic reaction was observed. After cooling for 3 hours,bis(2-methoxy-1-methylethyl)maleate (0.3% by weight, 9.9 g) was added todeactivate the Pt. The resulting polymer was isolated without strippingand gave a polymer of 1350 cP with a SiH content of 0.09 wt % (SiH asH). ²⁹Si NMR analysis of the product would demonstrate that all vinylfunctionality has been consumed yielding silethylene bridges, no ringopening has occurred and that the resulting molecular structure isconsistent with a methylhydrogen cyclic siloxane capped linear siloxanepolymer as described below, where Me is methyl, x is an average of 6.5for Mw and an average of 1.5 for Mn and d is an average of about 8.

EXAMPLE 5

To a reaction vessel was added 20.1 g of a poly(methylhydrogen)cyclosiloxane having an average Dp of about 4.4 (0.3 mol SiH) and 50 gof a dimethylvinylsiloxy end-blocked polydimethylsiloxane polymer havingan average Dp of about 60 (0.02 mol Vi) to give an SiH/SiVi ratio of15:1. The polymers were well mixed and a vinylsiloxane diluted Ptcatalyst added to give a Pt content of about 10 ppm. The typical andexpected exothermic reaction was observed. The resulting polymer wasstripped on a rotary evaporator to remove volatiles and was usedimmediately for performance evaluation without the Pt being deactivated.Titration showed that the product had an SiH level of 0.14 wt % (SiH asH). ²⁹Si NMR analysis of the product would demonstrate that all vinylfunctionality has been consumed yielding silethylene bridges, no ringopening has occurred and that the resulting molecular structure isconsistent with a methylhydrogen cyclic siloxane capped linear siloxanepolymer, where Me is methyl, x is an average of 1.5 for Mw and averageof 0 for Mn, and d is an average of about 8.

EXAMPLE 6

To a reaction vessel was added 297.1 g of a poly (methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (5.0 moles ofSiH) and 155.3 g of a vinyl endblocked polmer having an average Dp ofabout 25 (0.15 moles vinyl) to give a SiH/SiVi ratio of 33:1. Thepolymers were well mixed and a vinylsiloxane diluted Platinum (Pt)catalyst added to give a Pt content of about 12 ppm. The exothermicreaction resulted in a small to moderate temperature increase. Afterallowing the sample to cool for a few hours,bis(2-methoxy-1-methylethyl)maleate (0.4 g, 1 wt %.) was added tostabilize the Pt from further activity. The resulting polymer wasstripped on a rotovap at 1 mm Hg and 50 degrees Celsius to remove anyunreacted MeH cyclics. The isolated product had a viscosity of 49 mPa·s,a SiH level of 0.28 wt % (SiH as H) as determined by titration andmolecular weight as measured by GPC of Mn=2518 and Mw=33550 versuspolydimethylsiloxane (PDMS) standards. ²⁹Si and ¹³C NMR analysis of theproduct demonstrated that all vinyl functionality has been consumedyielding silethylene bridges, no ring opening had occurred and that theresulting molecular structure is consistent with a methylhydrogen cyclicsiloxane capped linear siloxane polymer as described below, where Me ismethyl, x corresponds to 10 for Mw, 0 for Mn and d is an average ofabout 25.

EXAMPLE 7

To a reaction vessel was added 279.0 g of a poly (methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (4.7 moles ofSiH) and 175.0 g of 30 dp OH— endblocked polymer (0.16 mol OH) to givean SiH/SiOH ratio of 30:1. The polymers were well mixed and avinylsiloxane diluted Platinum (Pt) catalyst added to give a Pt contentof about 12 ppm. The exothermic reaction resulted in a small to moderatetemperature increase. After allowing the sample to cool for a few hours,bis(2-methoxy-1-methylethyl)maleate (0.40 g, 1 wt %) was added tostabilize the Pt from further activity. The resulting polymer wasstripped on a rotovap at 1 mm Hg and 50 degrees Celsius to remove anyunreacted poly(methylhydrogen) cyclic siloxane. The isolated product hada viscosity of 422 mPa·s, a SiH level of 0.22 wt % (SiH as H) asdetermined by titration and a molecular weight as determined by GPC ofMn=5510 and Mw=65260 vs. polydimethylsiloxane (PDMS) standards. ²⁹Si and¹³C NMR analysis of the product demonstrated that all OH functionalityhad been consumed yielding SiO_(3/2) structural units (T), no ringopening had occurred and that the resulting molecular structure isconsistent with a methylhydrogen cyclic siloxane capped linear siloxanepolymer as described below, where Me is methyl, x is an average of 18for Mw, an average of 1.5 for Mn and d is an average of about 30.

EXAMPLE 8

To a reaction vessel was added 272.6 g of a poly (methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (4.5 moles ofSiH) and 175.0 g of a vinyldimethylsiloxy endblockedpoly(dimethylsiloxane-silicate) copolymer having an average dp of 100(0.093 mol vinyl) to give an SiH/SiVi ratio of 49:1. The polymers werewell mixed and a vinylsiloxane diluted Platinum (Pt) catalyst added togive a Pt content of about 12 ppm. The exothermic reaction resulted in asmall to moderate temperature increase. After allowing the sample tocool for a few hours, bis(2-methoxy-1-methylethyl)maleate (0.39 g, 1 wt%) was added to stabilize the Pt from further activity. The resultingpolymer was stripped on a rotovap at 1 mm Hg and 50 degrees Celsius toremove any unreacted MeH cyclics. The isolated product had a viscosityof 263 mPa·s, a SiH level of 0.15 wt % (SiH as H) as determined bytitration and a molecular weight as determined by GPC of Mn=5615 andMw=30030 vs. polydimethylsiloxane (PDMS) standards. ²⁹Si and ¹³C NMRanalysis of the product demonstrates that all vinyl functionality hadbeen consumed yielding silethylene bridges, no ring opening had occurredand that the resulting nominal Mn molecular structure is consistent witha methylhydrogen cyclic siloxane capped siloxane polymer as describedbelow, where Me is methyl and d is about 25. Oligomers of this structurecan of course grow from any or all of the arms.

EXAMPLE 9

To a reaction vessel was added 238.2 g of a poly (methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (4.0 moles ofSiH) and 175.0 g of an endblocked and vinyl pendant polydimethylsiloxanecopolymer (0.08 mol vinyl) to give an SiH/SiVi ratio of 50:1. Thepolymers were well mixed and a vinylsiloxane diluted Platinum (Pt)catalyst added to give a Pt content of about 12 ppm. The exothermicreaction resulted in a small to moderate temperature increase. Afterallowing the sample to cool for a few hours,bis(2-methoxy-1-methylethyl)maleate (0.39 g, 1 wt %) was added tostabilize the Pt from further activity. The resulting polymer wasstripped on a rotovap at 1 mm Hg and 50 degrees Celsius to remove anyunreacted MeH cyclics. The isolated product had a viscosity of 295mPa·s, a SiH level of 0.15 wt % (SiH as H) as determined by titrationand a molecular weight as measured by GPC of Mn=6872 and Mw 21960 vs.polydimethylsiloxane (PDMS) standards. ²⁹Si and ¹³C NMR analysis of theproduct demonstrates that all vinyl functionality had been consumedyielding silethylene bridges, no ring opening had occurred and that theresulting nominal Mn molecular structure is consistent with amethylhydrogen cyclic siloxane capped pendant and endblocked PDMSsiloxane polymer as described below, where Me is methyl, d₁ is about 97and d₂ is about 1.3. Oligomers of this structure can grow from theendblocked or pendant arms.

EXAMPLE 10

To a reaction vessel was added 236.1 g of a poly (methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (3.9 moles ofSiH) and 175.0 g of an endblocked and hexenyl pendantpolydimethylsiloxane copolymer (0.076 mol vinyl) to give an SiH/SiViratio of 52:1. The polymers were well mixed and a vinylsiloxane dilutedPlatinum (Pt) catalyst added to give a Pt content of about 12 ppm. Theexothermic reaction resulted in a small to moderate temperatureincrease. After allowing the sample to cool for a few hours,bis(2-methoxy-1-methylethyl)maleate (0.39 g, 1 wt %) was added tostabilize the Pt from further activity. The resulting polymer wasstripped on a rotovap at 1 mm Hg and 50 degrees Celsius to remove anyunreacted poly(methylhydrogen) cyclic siloxane. The isolated product hada viscosity of 284 mPa·s, a SiH level of 0.17 wt % (SiH as H) asdetermined by titration and a molecular weight as determined by GPC ofMn=4282 and Mw=17290 vs. polydimethylsiloxane (PDMS) standards. ²⁹Si and¹³C NMR analysis of the product demonstrated that all vinylfunctionality had been consumed yielding silethylene bridges, no ringopening had occurred and that the resulting nominal Mn molecularstructure is consistent with a methylhydrogen cyclic siloxane cappedendblocked and pendant siloxane polymer as described below, where Me ismethyl, d₁ is about 97 and d₂ is about 1.3.

EXAMPLE 11

To a reaction vessel was added 289.7 g of a poly (methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (4.8 moles ofSiH) and 175.0 g of a trimethylsiloxy endblocked, vinyl pendantpolydimethylsiloxane copolymer having an average Dp of about 165 (0.089mol vinyl) to give an SiH/SiVi ratio of 54:1. The polymers were wellmixed and a vinylsiloxane diluted Platinum (Pt) catalyst added to give aPt content of about 12 ppm. The exothermic reaction resulted in a smallto moderate temperature increase. After allowing the sample to cool fora few hours, bis(2-methoxy-1-methylethyl)maleate (0.40 g, 1 wt %) wasadded to stabilize the Pt from further activity. The resulting polymerwas stripped on a rotovap at 1 mm Hg and 50 degrees Celsius to removeany unreacted poly(methylhydrogen) cyclics; The isolated product had aviscosity of 1020 mPa·s, a SiH level of 0.19 wt % (SiH as H) asdetermined by titration and a molecular weight as determined by GPC ofMn=8902 and Mw=60370 vs polydimethylsiloxane (PDMS) standards. ²⁹Si and¹³C NMR analysis of the product demonstrates that all vinylfunctionality had been consumed yielding silethylene bridges, no ringopening had occurred and that the resulting nominal Mn molecularstructure is consistent with a methylhydrogen cyclic siloxane cappedvinyl pendant siloxane polymer as described below, where Me is methyl,d₁ is about 157 and d₂ is about 6.

EXAMPLE 12

To a reaction vessel was added 233.9 g of a poly (methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (3.9 moles ofSiH) and 175.0 g of a trimethylsiloxy endblocked, hexenyl pendantpolydimethylsiloxane copolymer (0.076 mol vinyl) to give an SiH/SiViratio of 51:1. The polymers were well mixed and a vinylsiloxane dilutedPlatinum (Pt) catalyst added to give a Pt content of about 12 ppm. Theexothermic reaction resulted in a small to moderate temperatureincrease. After allowing the sample to cool for a few hours,bis(2-methoxy-1-methylethyl)maleate (0.39 g, 1 wt %) was added tostabilize the Pt from further activity. The resulting polymer wasstripped on a rotovap at 1 mm Hg and 50 degrees Celsius to remove anyunreacted poly(methylhydrogen) cyclic. The isolated product had aviscosity of 585 mPa·s, a SiH level of 0.15 wt % (SiH as H) asdetermined by titration and a molecular weight as determined by GPC ofMn=7930 and Mw=50100 vs polydimethylsiloxane (PDMS) standards. ²⁹Si and¹³C NMR analysis of the product demonstrated that all vinylfunctionality had been consumed yielding silethylene bridges, no ringopening had occurred and that the resulting nominal Mn molecularstructure is consistent with a methylhydrogen cyclic siloxane cappedpendant siloxane polymer as described below, where Me is methyl, d₁ isabout 143 and d₂ is about 5.

EXAMPLE 13

To a reaction vessel was added 654.0 g of a poly (methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (6.9 moles ofSiH) and 110.0 g of a hexenyl endblocked polydimethylsiloxane polymer(0.25 mol vinyl) to give an SiH/SiVi ratio of 44:1. The polymers werewell mixed and a vinylsiloxane diluted Platinum (Pt) catalyst added togive a Pt content of about 12 ppm. The exothermic reaction resulted in asmall to moderate temperature increase. After allowing the sample tocool for a few hours, bis(2-methoxy-1-methylethyl)maleate (0.39 g, 1 wt%) was added to stabilize the Pt from further activity. The resultingpolymer was stripped on a rotovap at 1 mm Hg and 50 degrees Celsius toremove any unreacted poly(methylhydrogen) cyclic siloxane. The isolatedproduct had a viscosity of 29 mPa·s, a SiH level of 0.50 wt % (SiH as H)as determined by titration and a molecular weight as determined by GPCof Mn=1648 and Mw=16060 vs polydimethylsiloxane (PDMS) standards. ²⁹Siand ¹³C NMR analysis of the product demonstrated that all vinylfunctionality has been consumed yielding silethylene bridges, no ringopenings had occurred and that the resulting molecular structure isconsistent with a methylhydrogen cyclic siloxane capped linear siloxanepolymer as described below, where Me is methyl, x corresponds to 8 forMw, 0 for Mn and d is an average of about 10.

EXAMPLE 14

To a reaction vessel was added 837.0 g of a poly (methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (14.0 moles ofSiH) and 65.0 g of tetrakis(vinyldimethylsiloxy)silane (0.60 mol vinyl)to give an SiH/SiVi ratio of 23:1. The polymers were well mixed and avinylsiloxane diluted Platinum (Pt) catalyst added to give a Pt contentof about 12 ppm. The exothermic reaction resulted in a small to moderatetemperature increase. After allowing the sample to cool for a few hours,bis(2-methoxy-1-methylethyl)maleate (0.40 g, wt %) was added tostabilize the Pt from further activity. The resulting polymer wasstripped on a rotovap at 1 mm Hg and 50 degrees Celsius to remove anyunreacted poly(methylhydrogen) cyclic siloxane. The isolated product hada viscosity of 81 mPa·s, a SiH level of 0.90 wt % (SiH as H) asdetermined by titration and a molecular weight as determined by GPC ofMn=1460 and Mw=18600 vs polydimethylsiloxane (PDMS) standards. ²⁹Si and¹³C NMR analysis of the product demonstrated that all vinylfunctionality has been consumed yielding silethylene bridges, no ringopening had occurred and that the resulting nominal molecular structurefor Mn is consistent with a methylhydrogen cyclic siloxane cappedsiloxane polymer as described below, where Me is methyl. Higheroligomers can grow from any of the branches.

EXAMPLE 15

To a reaction vessel was added 729.7 g of a poly (methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (12.2 moles ofSiH) and 85.0 g of tetrakis(hexenyldimethylsiloxy)silane (0.52 molvinyl) to give an SiH/SiVi ratio of 24:1. The polymers were well mixedand a vinylsiloxane diluted Platinum (Pt) catalyst added to give a Ptcontent of about 12 ppm. The exothermic reaction resulted in a small tomoderate temperature increase. After allowing the sample to cool for afew hours, bis(2-methoxy-1-methylethyl)maleate (0.40 g, wt %) was addedto stabilize the Pt from further activity. The resulting polymer wasstripped on a rotovap at 1 mm Hg and 50 degrees Celsius to remove anyunreacted poly(methylhydrogen) cyclic. The isolated product had aviscosity of 32 mPa·s, a SiH level of 0.70 wt % (SiH as H) as determinedby titration and a molecular weight as determined by GPC of Mn=1453 andMw=27690 vs polydimethylsiloxane (PDMS) standards. ²⁹Si and ¹³C NMRanalysis of the product demonstrated that all vinyl functionality hasbeen consumed yielding silethylene bridges, no ring opening had occurredand that the resulting nominal molecular structure for Mn is consistentwith a methylhydrogen cyclic siloxane capped siloxane polymer asdescribed below, where Me is methyl. Higher oligomers can grow from anyof the branches.

EXAMPLE 16

To a reaction vessel was added 381.1 g of a poly(methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (6.3 moles SiH)and 80.0 g of a dimethylvinylsiloxy end-blocked polydimethylsiloxanepolymer having an average Dp of about 7 (0.29 moles vinyl) to give anSiH/SiVi ratio of about 22:1. The polymers were well mixed and avinylsiloxane diluted platinum (Pt) catalyst was added to give a Ptcontent of about 4 ppm. An exotherm reaction was initiated and over aperiod of 10 minutes the temperature of the vessel contents rose toabove room temperature. After cooling for 2 hours, the resulting polymerwas stripped in a rotovap at 1 mm Hg and 95 C to remove any unreactedpoly(methylhydrogen) cyclic siloxane. The material was then allowed tocool to room temperature. After cooling, 150 g of above product wasadded to another reaction vessel. Then 24.3 g (0.29 moles vinyl) of1-hexene was slowly added to the reaction vessel. An exothermic reactionwas initiated with each small addition. After cooling for 2 hours,bis(2-methoxy-1-methylethyl)maleate (0.87 g, 0.5 wt %) was added tostabilize the Pt from further activity. The resulting polymer was thenstripped a second time in a rotovap at 1 mm Hg and 95 C to remove anyunreacted 1-hexene. After cooling to room temperature,bis(2-methoxy-1-methylethyl)maleate (0.87 g, 0.5 wt %) was added tostabilize the Pt from further activity. The material was then allowed tocool to room temperature. The isolated product had a viscosity of 62mPa·s, a SiH level of 0.32% (SiH as H) as determined by titration and aGPC Mn=1723 and Mw=15640 versus polydimethylsiloxane (PDMS) standards.²⁹Si NMR analysis of the product demonstrates that all vinylfunctionality has been consumed yielding silethylene bridges, no ringopenings has occurred and that the resulting molecular structure isconsistent with a methylhydrogen cyclic siloxane capped linear siloxanepolymer as described below, where x is about 1 for Mn, about 9 for Mwand d is an average of about 7.

EXAMPLE 17

To a reaction vessel was added 737 g of a poly(methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (12.2 molesSiH) and 1263 g of a dimethylvinylsiloxy end-blockedpolydimethylsiloxane polymer having an average Dp of about 8 (3.6 molesvinyl) to give an SiH/SiVi ratio of 3.4:1. The polymers were well mixedand a vinylsiloxane diluted platinum (Pt) catalyst added to give a Ptcontent of about 4 ppm. An exothermic reaction was initiated and over aperiod of 10 minutes the temperature of the vessel contents rose from25° C. to 137° C. After the reaction mixture had cooled to 25 C, 91.1 g(0.80 mol) allylglycidylether (AGE) was added. The reaction was thenheated via heating mantle to 50 C at which point the heat was turnedoff. The reaction mixture continued to exotherm to 66 C over 5 minutesand held steady at 66 C for an additional 5 minutes. Analysis by gaschromatography at this point showed no trace of the AGE raw material.When the temperature began to drop, the heat was turned back on and thereaction mixture was maintained at 80 C for 2 hours. The reaction wasthen allowd to cool to 25 C. To stabilize the product, 4.2 g (0.2 wt. %)bis(2-methoxy-1-methylethyl)maleate was then added. The isolated producthad a viscosity of 93 mPa·s, a SiH level of 0.36% (SiH as H) asdetermined by titration and a GPC Mn=2626 and Mw=6405 versuspolydimethylsiloxane (PDMS) standards. The structure is shown below,where 10% of the SiH functions have been replaced with apropylglycidylether group, x=1-5 and d=about 8.

EXAMPLE 18

To a reaction vessel was added 737.0 g of a poly(methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (12.2 molesSiH) and 1263.0 g of a dimethylvinylsiloxy end-blockedpolydimethylsiloxane polymer having an average Dp of about 8 (3.6 molesvinyl) to give an SiH/SiVi ratio of 3.4:1. The polymers were well mixedand a vinylsiloxane diluted platinum (Pt) catalyst added to give a Ptcontent of about 4 ppm. An exothermic reaction was initiated and over aperiod of 10 minutes the temperature of the vessel contents rose from25° C. to 137° C. After the reaction mixture had cooled to 25 C, 227.9 g(2.0 mol) AGE was added. The reaction was then heated via heating mantleto 50 C at which point the heat was turned off. The reaction mixturecontinued to exotherm to 91 C over 10 minutes. Analysis by gaschromatography at this point showed no trace of the AGE raw material.When the reaction temperature had dropped back to 80 C, the heat wasturned back on and the reaction mixture was maintained at 80 C for 2hours. The reaction was then allowd to cool to 25 C. To stabilize theproduct, 4.2 g (0.2 wt. %) bis(2-methoxy-1-methylethyl)maleate was thenadded. The isolated product had a viscosity of 85 mPa·s, a SiH level of0.30% (SiH as H) as determined by titration and a GPC Mn=2867 andMw=7561 versus polydimethylsiloxane (PDMS) standards. The structure isshown below, where 25% of the SiH functions have been replaced with apropylglycidylether group, x=1-5 and d=about 8.

Preparation of Coatings

Coatings were formulated at a 1.6:1 SiH:Vi ratio using vinylsiloxanediluted platinum (Pt) (catalyst), bis (2-methoxy-1-methylethyl) maleate(inhibitor), a dimethylvinylsiloxy end-blocked polydimethylsiloxane(PDMS) polymer with an average degree of polymerization of 130 (P-1),and either a organohydrogensilicon compound crosslinker prepared viaExamples 1-18 or a comparative crosslinker selected from (C-1) atrimethylsiloxy end-blocked polydimethylsiloxane-methylhydrogensiloxanecopolymer having a total average degree of polymerization of about 40with about 70 mol % methylhydrogen moiety on the siloxane chain or (C-2)a trimethylsiloxy end-blocked poly(methylhydrogen) siloxane polymerhaving a total average degree of polymerization of about 20. Theformulations were prepared by mixing the dimethylvinylsiloxy end-blockedpolydimethylsiloxane (PDMS) polymer, the SiH containing material and theinhibitor in a jar and then adding the platinum catalyst with mixing toform each coating formulation. Each formulation was then coated ontopaper at a thickness of approximately 1.5 microns, as measured by X-rayfluorescence (XRF) on an Oxford Lab-X3000 Benchtop XRF Analyzer, andcured on a moving web at a temperature of 300° F. for 6 sec. Amounts ofcatalyst and inhibitor used and bath life measurements are provided inTable 1 and cure comparison measurements are found in Table 2.

TABLE 1 Bath life Comparison of Coatings Platinum Level (ppm) 100 100 6020 20 Inhibitor Level (%) 0.1 0.7 0.4 0.1 0.7 Bath Life (hours) withCrosslinker from: Example 1 58 340 360 230 1350 C-1* 0.06 22 10 1.1 104C-2* 0.05 14 6 0.8 105 Example 6 14 Example 7 0.33 Example 8 14 Example9 14 Example 10 14 Example 11 0.25 Example 12 5 Example 13 5 Example 140.5 Example 15 6 Example 16 12 Example 17 1.0 Example 18 5.4*comparative

TABLE 2 Cure Comparison of Coatings Platinum Level (ppm) 100 60 20 20 2010 5 Inhibitor Level (%) 0.7 0.4 0.1 0.4 0.7 0.4 0.4 % ExtractableSilicone with Crosslinker from: Example 1 3 4 4 3 4 2 6 Example 2 3 5 4Example 3 2 4 Example 4 2 2 Example 5 3 17 Example 6 2 4 42 Example 7 210 Example 8 2 4 20 Example 9 3 8 Example 10 2 8 Example 11 4 10 Example12 4 6 Example 13 4 14 Example 14 7 25 Example 15 3 9 Example 16 4 4 8Example 17 3 Example 18 2 C-1* 3 4 4 8 12 40 C-2* 3 5 27 25 43 75 94*comparative

Adhesion Testing: To test for adhesion under high temperature andhumidity, coatings were formulated at a 1.6:1 SiH:Vi ratio usingvinylsiloxane diluted platinum (Pt) (catalyst), bis(2-methoxy-1-methylethyl) maleate (inhibitor), a polymer chosen fromeither a dimethylvinylsiloxy end-blocked polydimethylsiloxane (PDMS)polymer with an average degree of polymerization of 130 (P-1) or avinyldimethylsiloxy endblocked poly(dimethylsiloxane-silicate) copolymerhaving an average Dp of about 160 (P-2), and either theorganohydrogensilicon compound prepared via Example 18 or a comparativecrosslinker (C-2) a trimethylsiloxy end-blocked poly(methylhydrogen)siloxane polymer having a total average degree of polymerization ofabout 20. The formulations were prepared by mixing the appropriatepolymer, SiH containing material and inhibitor in a jar and then addingthe platinum catalyst with mixing to form each coating formulation. Thecoatings were then coated onto paper at a thickness of approximately 1.5microns, and cured on a moving web to less than 5 percent extractablesilicone. The cured coatings were then laminated with an acrylicemulsion adhesive and aged in a climate-controlled chamber that wasmaintained at 150 degrees F. and 85 percent relative humidity. Theadhesion of the release coating to the substrate was periodicallymeasured by a finger rub-off test. A designation of “Y” was assigned ifrub-off was observed, indicating poor adhesion, and a designation of “N”was assigned if no rub-off was observed, indicating good adhesion. SeeTable 3 for the results.

TABLE 3 Adhesion of Coatings to Substrate After High Temperature andHumidity Aging Finger Rub-off (Y/N) Period of Aging (Days): PolymerCrosslinker Pt Level Substrate 0 1 7 P-1 Example 18 20 Glassine N N NP-1 C-2* 100 Glassine N N Y P-2 Example 18 20 Glassine N N N P-2 C-2* 20Glassine N Y *comparative

1. A composition comprising (A) at least one compound having at leastone aliphatic unsaturation; (B) at least one organohydrogensiliconcompound containing at least one silicon-bonded hydrogen atom permolecule described by formula (III)

where each R is independently selected from a hydrogen atom and amonovalent hydrocarbon group comprising 1 to 20 carbon atoms which isfree from aliphatic unsaturation, a is an integer from 1 to 18, b is aninteger from 1 to 19, a+b is an integer from 3 to 20, each X is anindependently selected functional group selected from a halogen atom, anether group, an alkoxy group, an alkoxyether group, an acyl group, anepoxy group, an amino group, or a silyl group, or a -Z-R⁴ group, whereeach Z is independently selected from an oxygen and a divalenthydrocarbon group comprising 2 to 20 carbon atoms, each R⁴ group isindependently selected from —BR_(u)Y_(2-u), or a group described byformula (IV):(Y_(3-n)R_(n)SiO_(1/2))_(c)(Y_(2-o)R_(o)SiO_(2/2))_(d)(Y_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)Y_(1-q))_(g)(CR_(r)Y_(2-r))_(h)(O(CR_(s)Y_(2-s)))_(i)(CR_(t)Y_(3-t))_(j)where B refers to boron, each R is as described above, the sum ofc+d+e+f+g+h+i+j is at least 2, n is an integer from 0 to 3, o is aninteger from 0 to 2, p is an integer from 0 to 1, q is an integer from 0to 1, r is an integer from 0 to 2, s is an integer from 0 to 2, t is aninteger from 0 to 3, u is an integer from 0 to 2, each Y is anindependently selected functional group selected from a halogen atom, anether group, an alkoxy group, an alkoxyether group, an acyl group, anepoxy group, an amino group, or a silyl group, or a Z-G group, where Zis as described above, each G is a cyclosiloxane described by formula(V):

where R and X are as described above, k is an integer from 0 to 18, m isan integer from 0 to 18, k+m is an integer from 2 to 20, provided informula (IV) that one of the Y groups is replaced by the Z group bondingthe R⁴ group to the cyclosiloxane of formula (III), and provided furtherat least one X group of formula (III) is a -Z-R⁴ group, if g+h+f+i+j>0then c+d+e+f>0 and if Z is a divalent hydrocarbon group, a=1, c=2,e+f+g+h+i+j=0 and d>0, then at least one d unit (ie.Y_(2-o)R_(o)SiO_(2/2)) contain a -Z-G group or the c units (ie.Y_(3-n)R_(n)SiO_(1/2)) have no -Z-G group or at least two -Z-G groups;and (C) a platinum group metal-containing catalyst.
 2. The compositionof claim 1 where subscript b is an integer from 2 to 19, subscript c isan integer from 0 to 50, subscript d is an integer from 0 to 5000,subscript e is an integer from 0 to 48, subscript f is an integer from 0to 24, subscript g is an integer from 0 to 50, subscript h is an integerfrom 0 to 50, subscript i is an integer from 0 to 50, and subscript j isan integer from 0 to
 50. 3. The composition of claim 1 where subscript cis an integer from 2 to 15, subscript d is an integer from 0 to 1000,subscript e is an integer from 0 to 13, subscript f is an integer from 0to 6, subscript g is an integer from 0 to 20, subscript h is an integerfrom 0 to 20, subscript i is an integer from 0 to 20, subscript j is aninteger from 0 to
 15. 4. The composition of claim 1 where each R groupis independently selected from hydrogen atoms, alkyl groups comprising 1to 8 carbon atoms, or aryl groups comprising 6 to 9 carbon atoms, each Xis a Z-R⁴ group or is independently selected from chloro, methoxy,isopropoxy, and groups derived by hydrosilylation of the alkenyl groupfrom hydroxybutylvinyl ether, vinylcyclohexylepoxide, andallylglycidylether with an SiH from the siloxane precursor to formulas(III) or (V), where Z is a divalent hydrocarbon group, and R⁴ isselected from —R₂SiO(R₂SiO)_(d)SiR₂-Z-G, —R₂SiOSiR₃, —R₂SiOSiR₂—Y,—RSi(OSiR₃)₂, where d is an integer from 1 to 50 and Z, G, and R are asdescribed above.
 5. The composition of claim 1 where each R group isindependently selected from hydrogen, methyl, alpha-methylstyryl,3,3,3-trifluoropropyl and nonafluorobutylethyl.
 6. The composition ofclaim 1 where R is methyl, and d is an average of
 8. 7. The compositionof claim 1 where component (B) is described by the structure below whereMe is methyl, d is an average of 8, and x is an integer from 1 to
 15.


8. The composition of claim 1 where such organohydrogensilicon compoundscontain at least 2 silicon-bonded hydrogen atoms per molecule.
 9. Thecomposition of claim 1 where such organohydrogensilicon compoundscontain at least 3 silicon-bonded hydrogen atoms per molecule.
 10. Thecomposition of claim 1 where such compounds have a viscosity from 5 to50,000 mPa·s.
 11. The composition of claim 1 where component (A) isselected from trimethylsiloxy-terminatedpolydimethylsiloxane-polymethylvinylsiloxane copolymers,vinyldimethylsiloxy-terminatedpolydimethylsiloxane-polymethylvinylsiloxane copolymers,trimethylsiloxy-terminatedpolydimethylsiloxane-polymethylhexenylsiloxane copolymers,hexenyldimethylsiloxy-terminatedpolydimethylsiloxane-polymethylhexenylsiloxane copolymers,vinyldimethylsiloxy-terminatedpolydimethylsiloxane-polymethyhexenylsiloxane copolymers,trimethylsiloxy-terminated polymethylvinylsiloxane polymers,trimethylsiloxy-terminated polymethylhexenylsiloxane polymers,vinyldimethylsiloxy-terminated polydimethylsiloxane polymers, andhexenyldimethylsiloxy-terminated polydimethylsiloxane polymers,vinyldimethylsiloxy terminatedpoly(dimethylsiloxane-monomethylsilsesquioxane) polymers,vinyldimethylsiloxy terminatedpoly(dimethylsiloxane-vinylmethylsiloxane-methylsilsesquioxane)copolymers; trimethylsiloxy terminatedpoly(dimethylsiloxane-vinylmethylsiloxane-methylsilsesquioxane)polymers, hexenyldimethylsiloxy terminatedpoly(dimethylsiloxane-monomethylsilsesquioxane) polymers,hexenyldimethylsiloxy terminatedpoly(dimethylsiloxane-hexenylmethylsiloxane-methylsilsesquioxane)copolymers; trimethylsiloxy terminatedpoly(dimethylsiloxane-hexenylmethylsiloxane-methylsilsesquioxane)polymers, vinyldimethylsiloxy terminated poly(dimethylsiloxane-silicate)copolymers, hexenyldimethylsiloxy-terminatedpoly(dimethylsiloxane-silicate) copolymers, trimethylsiloxy terminatedpoly(dimethylsiloxane-vinylmethylsiloxane-silicate) copolymers andtrimethylsiloxy terminatedpoly(dimethylsiloxane-hexenylmethylsiloxane-silicate) copolymers,vinylsiloxy or hexenylsiloxy terminatedpoly(dimethylsiloxane-hydrocarbyl copolymers), vinylsiloxy terminated orhexenylsiloxy terminated poly(dimethylsiloxane-polyoxyalkylene) blockcopolymers, alkenyloxydimethylsiloxy terminated polyisobutylene andalkenyloxydimethylsiloxy terminated polydimethylsiloxane-polyisobutyleneblock copolymers.
 12. The composition of claim 1 further comprising (D)an inhibitor.
 13. The composition of claim 1 further comprising (E) abath life extender.
 14. The composition of claim 1 further comprising(F) a release additive.
 15. The composition of claim 1 where component(A) comprises at least one compound having at least two aliphaticunsaturations.
 16. A method of making a cured coating comprising thesteps of (I) mixing: (A) at least one compound having at least twoaliphatic unsaturations of claim 15; (B) at least oneorganohydrogensilicon compound containing at least three silicon-bondedhydrogen atom per molecule of claim 13 and (C) a platinum groupmetal-containing catalyst which is present in an amount sufficient tocatalyze the reaction; (II) coating the mixture from (I) on the surfaceof a substrate; and (III) exposing the coating and the substrate to anenergy source selected from (i) heat and (ii) actinic radiation in anamount sufficient to cure the coating.
 17. The method of claim 16further comprising (IV) applying a pressure sensitive adhesive on thecoating after step (III).
 18. The cured coating prepared by the methodof claim
 16. 19. The cured coating prepared by the method of claim 17.20. The composition of claim 1 where component (B) is selected from thestructures below where Me is methyl, d¹+d²=d, and x can range from 1 to100:


21. The composition of claim 20 or where component (B) is described bysuch structures where 5 to 70 percent of the SiH bonds are replaced byhydrocarbon, oxyhydrocarbon or functional groups.
 22. The composition ofclaim 20 where component (B) is described by such structures where 5 to50 percent of the SiH bonds are replaced by functional groups derived byhydrosilylation of allylglycidyl ether (propylglycidyl ether groups) orvinylcyclohexylepoxide, alkyl groups or alkenyl groups.
 23. Thecomposition of claim 20 where component (B) is described by suchstructures where 10 to 30 percent of the SiH bonds are replaced byfunctional groups derived by hydrosilylation of allylglycidyl ether(propylglycidyl ether groups).